CN109216675A

CN109216675A - A kind of lithium battery material and its preparation method and application that copper nitride is modified

Info

Publication number: CN109216675A
Application number: CN201811031567.XA
Authority: CN
Inventors: 李泉; 李文俊; 禹习谦; 李泓
Original assignee: Institute of Physics of CAS; Beijing WeLion New Energy Technology Co ltd
Current assignee: Institute of Physics of CAS; Beijing WeLion New Energy Technology Co ltd
Priority date: 2018-09-05
Filing date: 2018-09-05
Publication date: 2019-01-15

Abstract

The present invention provides a copper nitride modified lithium battery material, a preparation method and application thereof, wherein the lithium battery material comprises a lithium battery base material and is coated on the surface of the lithium battery base material or incorporated with the lithium The copper nitride in the battery base material, wherein the chemical formula of the copper nitride is Cu AN, wherein _0.5≤A≤4 . The copper nitride-modified lithium battery material provided by the invention can effectively inhibit the growth of lithium dendrites in the lithium battery and improve the cycle performance. The battery provided by the invention has better safety, cycle life, power density, rate performance, energy efficiency and storage life.

Description

A kind of lithium battery material and its preparation method and application that copper nitride is modified

Technical field

The present invention relates to novel energy resource material technology, lithium battery material technology and electrode interface technical field of modification, especially relate to And a kind of lithium battery material and its preparation method and application that copper nitride is modified.

Background technique

Lithium battery has highest energy density in current all commercial batteries, is widely used in consumer electronics, electronic The fields such as automobile, scale energy storage.In recent years, the fast development of every profession and trade is to battery life, energy density, high rate performance and safety Property made higher requirement.

The capacity that graphite cathode is discharged in production has been approached its theoretical limit, contains silicium cathode and composition metal cathode of lithium It is the optional cathode of the following battery with high theoretical capacity.But containing silicium cathode and lithium anode in cyclic process In exist very big volume expansion, cause the SEI of negative terminal surface constantly rupture and regenerate, substantially reduce battery coulomb imitate Rate and cycle life.Especially lithium anode unevenly deposits, dissolves caused Li dendrite and high chemical reactivity (high activity) can also cause safety issue.Li dendrite and high activity are two coupling factors, and dendritic growth breaks through SEI and electrolysis Liquid further reacts；During discharge, the preferential dissolution of dendrite root lithium causes dendrite to be broken and form " dead lithium "；Li dendrite Length may penetrate diaphragm to a certain extent and cause short circuit.The problem of for high capacity cathode, generally use following scheme Or approach is handled: lithium metal combination electrode or lithium alloy, and ex situ coats organic inorganic world surface layer, and modified electrolyte is in situ Reaction, which generates, stablizes fine and close SEI layer, electrolysis additive, copolymer solid electrolyte, change charge and discharge mode, oxide, Sulfide solid electrolyte and lithium anode structure is modified to reduce effective current density and volume expansion.

Above scheme or approach are provided with certain effect, but also there is obvious disadvantage, always not by extensive quotient Industry application.Specifically, preparing lithium metal combination electrode need to be compound with lithium powder and carbon electrode, and the high reactivity of lithium powder is brought Dusting can occur after being circulated throughout for great security risk, lithium alloy；Utilize the method practical application for changing charge and discharge mode It is more difficult；Scheme modified for electrolyte, the processing preparation of nanostructure electrolyte is difficult, high salt concentration electrolyte wellability at high cost It is low；Liquid electrolytic solution additive is a kind of important method of modifying, such as Cs⁺The reactivity of additive is higher, but at high cost, and Lithium nitrate additive will lead to the release of the gases such as NO, and battery flatulence is caused even to be exploded；Double salt LiTFSI/LiFSI (LiTFSI is double trifluoromethanesulfonimide lithiums, and LiFSI is double fluorine sulfimide lithiums) or three salt LiTFSI/LiBOB/LiPF₆ Battery efficiency can be improved in (LiBOB is di-oxalate lithium borate) system, alleviates capacitance loss；VC, FEC and VEC etc. can effectively form a film, However the process, under long circulating, surface SEI still can rupture, electrolysis additive is generally consumption-type additive, follows in length Additive is always depleted after ring, influences the cycle performance of battery；High capacity is protected using polymer solid electrolyte material The main problem of cathode is that ionic conductivity is relatively low and mechanical performance is poor, and general electrochemical window is less than 3.8V, is not available Cobalt acid lithium, tertiary cathode material etc. have the positive electrode of high voltage, although by using linear or graft polymers solid Conductivity, and the better mechanical property of graft polymers, but higher cost, network polymers conductivity can be improved in electrolyte Also very small；Inorganic solid electrolyte has wider electrochemical window, and chemical environment is stablized, non-volatile, nonflammable, prevents The side reaction of high capacity cathode and solution, mechanical performance be high, under high pressure can be with smooth cathode, however inorganic solid electrolyte Conductivity is generally lower, and high rate performance is poor, due to the volume expansion of high capacity negative maximum, causes and inorganic solid electrolyte Physical contact is deteriorated, and anode equally exists big volume expansion, can also be deteriorated with the interface of solid electrolyte, there is also dendrite to wear Saturating safety problem, and expansion work can also reduce energy efficiency, furthermore solid oxide electrolyte poor toughness, frangible, battery Structure design has certain difficulty, as LiPON solid electrolyte, the sulfide solid mentioned in Chinese patent CN03115669 are electrolysed The interfacial instability of matter and positive electrode, high capacity cathode, needs to coat buffer layer, and sulfide electrolyte safety leaves a question open, Inorganic whisker electrolyte the problems such as there is also biggish interface impedances.

Summary of the invention

Therefore, the purpose of the present invention is to for above-mentioned technical problem present in this field, provide a kind of copper nitride to change Property lithium battery material and its preparation method and application, the modified lithium battery material of copper nitride provided by the invention can be effective Ground inhibits lithium battery lithium dendrite growth, and improves cycle performance.

The inventors discovered that having contained that the pair of graphite surface is anti-significantly by graphite particle surface coated copper nitride It answers, especially the growth of metal Li dendrite, and also there is the cycle performance improved.The present inventors have additionally discovered that not only can be Coated copper nitride on the negative electrode active material particle surface of such as graphite, but also can collector, negative electrode tab, diaphragm and It is coated on solid electrolyte sheet, even copper nitride is mixed in polymer/solid electrolyte, can equally be played above-mentioned Effect.

The purpose of the present invention is what is be achieved through the following technical solutions.

On the one hand, the lithium battery material modified the present invention provides a kind of copper nitride, the lithium battery material include lithium Cell basis material and the copper nitridation being coated in the lithium battery base material surface or the incorporation lithium battery basic material Object, wherein the chemical formula of the copper nitride is Cu_AN, wherein 0.5≤A≤4.

The lithium battery material provided according to the present invention, wherein the lithium battery basic material can be for selected from negative electrode tab, collection One of fluid, diaphragm, solid electrolyte sheet, negative electrode active material particle and inorganic solid electrolyte particle are a variety of, institute State the surface that copper nitride is coated on the lithium battery basic material.

The lithium battery material provided according to the present invention, wherein table of the copper nitride in the lithium battery basic material On face can in membrane form or the form of island structure exist.In some preferred embodiments, the copper nitride is in institute It states and is present as a film on the surface of lithium battery basic material, and in some preferred embodiments, the film can be One or more layers.

In some embodiments, the thickness or particle size range of the copper nitride on the lithium battery basic material are coated on For 1nm~30 μm.

The lithium battery material provided according to the present invention, wherein the lithium battery basic material can also be polymer solids Electrolyte, the copper nitride mix in the copolymer solid electrolyte.

In some embodiments, in terms of the weight of the lithium battery material, the incorporation of the copper nitride is 5~30 Weight %, preferably 7~15 weight %.

The lithium battery material provided according to the present invention, wherein formula Cu_AIn N, 1≤A≤4, it is highly preferred that 1.5≤A≤3.

The lithium battery material provided according to the present invention, wherein the lithium battery basic material is selected from negative electrode tab, afflux One of body, diaphragm and solid electrolyte sheet are a variety of.

In some embodiments, the thickness or particle size range of the copper nitride on the lithium battery basic material are coated on For 2nm~10 μm, preferably 20nm~2 μm, more preferably 100nm~1.5 μm.

The lithium battery material provided according to the present invention, wherein the example of suitable negative electrode tab includes but is not limited to: lithium metal Negative electrode tab, composition metal lithium cathode sheet such as have the composite metal lithium and lithium alloy negative electrode tab of three-dimensional framework.

In some embodiments, the example of suitable lithium alloy negative electrode tab includes but is not limited to: lithium boron alloy negative electrode tab, Lithium-aluminium alloy negative electrode tab and lithium magnesium alloy negative electrode tab.

The lithium battery material provided according to the present invention, wherein the example of suitable collector includes but is not limited to: copper foil, Punching copper mesh, foam copper, nickel foil, punching nickel screen and nickel foam.

The lithium battery material provided according to the present invention, wherein the collector with a thickness of 3 μm~5mm, preferably 5~ 50 μm, such as 12 μm.

The lithium battery material provided according to the present invention, wherein the example of suitable diaphragm includes but is not limited to: the poly- second of single layer Alkene (PE) diaphragm, single-layer polypropylene (PP) diaphragm, polyethylene-polypropylene-polyethylene (PE-PP-PE) three-layer membrane, polyimides (PI) diaphragm, poly- aramid fiber diaphragm, cellulosic separator and polyetherimide diaphragm.

The lithium battery material provided according to the present invention, wherein the solid electrolyte sheet be inorganic solid electrolyte piece or Copolymer solid electrolyte piece.

The lithium battery material provided according to the present invention, wherein the inorganic solid electrolyte piece is by selected from following inorganic One of solid electrolyte or a variety of formation: Li₅La₃Ta₂O₁₂、Li₅La₃Nb₂O₁₂、Li₇La₃Sn₂O₁₂、Li_1+xAl_xGe_2-x (PO₄)₃、Li_3yLa_2/3-yTiO₃、LiZr_2-zTi_z(PO₄)₃、Li_1+mAl_mTi_2-m(PO₄)₃、Li_4-nGe_1-nP_nS₄, LiPON electrolysis Matter (LiPON), Li_3+pSi_pP_pO₄、Li₇La₃Zr₂O₁₂、Li_7-qLa₃Zr_2-qTa_qO₁₂And Li₂S-P₂S₅System sulfide electrolyte；Its In, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0≤n≤1,0≤p≤2,0≤q≤1.

The lithium battery material provided according to the present invention, wherein the LiPON electrolyte can be Chinese patent Those of disclosed in CN03115669, it is herein incorporated by reference in the present invention.

The lithium battery material provided according to the present invention, wherein the polymer dielectric piece include polymer dielectric and Electrolytic salt.

The lithium battery material provided according to the present invention, wherein the example of suitable polymer dielectric includes but is not limited to: Polyethylene glycol oxide (PEO), polyphenylene oxide (PPO), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polystyrene (PS), poly- acetic acid second Enester (PVAC), polymethyl methacrylate (PMMA), polyimides (PI), poly- (vinylidene fluoride-hexafluoropropene) (PVDF- HFP), polyvinylpyrrolidone (PVP), poly- divinyl sulfide (PVS) and polyethyleneglycol diacrylate (PEGDA).

The lithium battery material provided according to the present invention, wherein the diaphragm with a thickness of 10~50 μm, preferably 15~20 μm。

The lithium battery material provided according to the present invention, wherein the porosity of the diaphragm be 10~50%, preferably 30~ 45%；

The lithium battery material provided according to the present invention, wherein the example of suitable electrolytic salt includes but is not limited to: LiPF₆, double trifluoromethanesulfonimide lithiums (LiTFSI), double fluorine sulfimide lithiums (LiFSI), LiNO₃、Li₂CO₃、LiF、 LiBF₄, di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), LiSO₃CF₃, (fluorine sulphonyl) (positive perfluoro butyl Sulphonyl) imine lithium (LiFNFSI) and LiClO₄One of or it is a variety of.

The lithium battery material provided according to the present invention, wherein the polymer dielectric piece with a thickness of 30~60 μm, with And porosity is 0~70%, preferably 0~10%.

The lithium battery material provided according to the present invention, wherein the example of suitable negative electrode active material particle includes but not It is limited to: silicon-based anode active material particle, for example, silicon-carbon cathode active material particle and silicon oxygen carbon activity material granule are as aoxidized Sub- silicon；Carbon based negative electrodes active material particle, for example, artificial graphite, natural graphite, hard carbon, soft carbon and carbonaceous mesophase spherules；Tinbase Negative electrode active material particle, for example, metallic tin and stannic oxide；Stratiform negative electrode active material particle, for example, lithium titanate and two sulphur Change molybdenum；And organic compound negative electrode active material particle, such as Li₂C₈H₄O₄。

The lithium battery material provided according to the present invention, wherein the example of suitable inorganic solid electrolyte particle include but It is not limited to: Li₅La₃Ta₂O₁₂、Li₅La₃Nb₂O₁₂、Li₇La₃Sn₂O₁₂、Li_1+xAl_xGe_2-x(PO₄)₃、Li_3yLa_2/3-yTiO₃、LiZr_2- _zTi_z(PO₄)₃、Li_1+mAl_mTi_2-m(PO₄)₃、Li_4-nGe_1-nP_nS₄, LiPON electrolyte, Li_3+pSi_pP_pO₄、Li₇La₃Zr₂O₁₂、 Li_7-qLa₃Zr_2-qTa_qO₁₂And Li₂S-P₂S₅System sulfide electrolyte；Wherein, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤ M≤2,0≤n≤1,0≤p≤2,0≤q≤1.

In some embodiments, in terms of the weight of the lithium battery material, the covering amount of the copper nitride is 0.02 ~2 weight %, preferably 0.05~1 weight %.

In some embodiments, the partial size D50 of the negative electrode active material particle is 2~20 μm, preferably 5~15 μ m；And in some embodiments, the partial size of copper nitride is 20nm~2 μm, preferably 100~500nm.

On the other hand, it the present invention provides the method for the preparation lithium battery material, the described method comprises the following steps:

(1) by vapor phase method, liquid phase method, solid phase method, cladding process, spray drying, electrostatic spinning or 3D printing in the lithium Coated copper nitride on cell basis material: or

(2) copper nitride is mixed into the lithium and mixing copper nitride with the component of the lithium battery basic material Cell basis material.

The method provided according to the present invention, wherein the example of suitable vapor phase method includes but is not limited to: magnetron sputtering, electricity Beamlet evaporation, thermal evaporation, atomic layer deposition (ALD), pulsed laser deposition (PLD), chemical vapor deposition (CVD) and plasma Enhance chemical vapor deposition.In some embodiments, the vapor phase method is magnetron sputtering method, electron beam evaporation method or atomic layer Sedimentation.

The method provided according to the present invention, wherein the example of suitable liquid phase method includes but is not limited to: hydrothermal/solvent heat Method, complexed-precipitation method, coprecipitation, sol-gal process and melt growth method.In some embodiments, the liquid phase method is total The precipitation method, sol-gal process or complexed-precipitation method.

The method provided according to the present invention, wherein the example of suitable solid phase method includes but is not limited to: powder solid phase method, Combustion method and machine-alloying.

Another aspect, the present invention provides a kind of lithium battery, the lithium battery includes at least one lithium battery material Material.

The lithium battery provided according to the present invention, wherein the lithium battery also includes positive electrode.In some embodiments In, the example of suitable positive electrode includes but is not limited to: LiFePO4, cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt aluminium Lithium, nickel ion doped, Li₂MnO₃、MnO₂、FeS₂、FeF₃、S、H₂O、CO₂And O₂。

The lithium battery provided according to the present invention, wherein the lithium battery may include electrolyte.

In some embodiments, the example suitable for the lithium salts of the electrolyte includes but is not limited to: LiPF₆, it is double Trifluoromethanesulfonimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI), LiNO₃、Li₂CO₃、LiF、LiBF₄, double oxalic acid Lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), LiSO₃CF₃, (fluorine sulphonyl) (positive perfluoro butyl sulphonyl) imine lithium (LiFNFSI)、LiClO₄。

In some embodiments, the example suitable for the solvent of the electrolyte includes but is not limited to: ethylene carbonate Ester (EC), polycarbonate (PC), vinylene carbonate) (VC, vinylethylene carbonate (VEC), polystyrene (PS), carbonic acid two Methyl esters (DMC), fluorinated ethylene carbonate (FEC), methyl ethyl carbonate (EMC), 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME)。

Another aspect is Cu the present invention also provides chemical formula_AThe copper nitride of N is inhibiting lithium battery especially lithium battery Negative terminal surface Li dendrite forms and/or improves the application in lithium battery cycle performance, wherein 0.2≤A≤4.

The lithium battery material provided according to the present invention, wherein formula Cu_AIn N, 0.5≤A≤4, it is preferable that 1≤A≤4, more Preferably, 1.5≤A≤3.

Present invention has the advantage that

(1) tool can be formed in situ in the copper nitride contained in lithium battery material provided by the invention in charge and discharge process There is the hybrid conductive network layer of electronic conductance and ionic conductance, electronic conductance and ionic conductance is homogenized, to metal Li dendrite Inhibitory effect is played in growth, reduces the generation of " dead lithium ", improves cycle performance, while can also reduce interface impedance.

(2) when being modified using copper nitride to negative electrode tab and negative electrode active material particle, the reaction of copper nitride in-situ The hybrid conductive dotcom world surface layer (SEI film) of generation is more stable, can protect cathode, prevents or alleviates further with electrolyte Reaction, improve cycle performance.Boundary layer can prevent cathode and electrolyte endlessly side reaction simultaneously, therefore can mention The stability at high electrode interface.

Particularly, it carries out copper nitride to the negative electrode active materials particle such as graphite to be modified, due to raw in situ in particle surface At there is the hybrid conductive network layer of electronic conductance and ionic conductance simultaneously, and then contain that the pair of particle surface is anti-significantly It answers, and also there is better high rate performance.In addition, the electronic conductance on surface still can induce lithium ion after embedding full lithium Deposition, fill up void among particles, so in situ formed lithium carbon composite electrode, can also greatly promote the appearance of cathode itself Amount, and original cycle life can be kept.

(3) the method for the present invention is cheap, easy, and is easy to amplify, can large-scale production the modified lithium battery material of copper nitride Material.

(4) battery provided by the invention possesses preferable safety, cycle life, power density, high rate performance, energy dose-effect Rate and storage life.

Detailed description of the invention

Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:

Figure 1A is a kind of structural schematic diagram of the modified membrane material of the copper nitride of embodiment according to the present invention；

Figure 1B is a kind of structural schematic diagram of the modified granular materials of the copper nitride of embodiment according to the present invention；

Fig. 2 is a kind of scanning electron microscope (SEM) photograph on the modified diaphragm material surface of the copper nitride of embodiment according to the present invention Piece；

Fig. 3 A is the scanning electron microscopic picture of rear surface of unmodified cathode charging；

Fig. 3 B is a kind of scanning of the modified cathode rear surface of charging of the copper nitride of embodiment according to the present invention Electron microscopic picture；

Fig. 4 A is the scanning electron microscopic picture of unmodified cathode charge and discharge after a week；

Fig. 4 B is a kind of scanning electricity of the modified cathode charge and discharge of the copper nitride of embodiment according to the present invention after a week Mirror picture；

Fig. 5 is the cathode and unmodified cathode that a kind of copper nitride of embodiment according to the present invention is respectively adopted and is modified The Symmetrical cells charging and discharging curve figure of assembly；

Fig. 6 is the diaphragm and unmodified diaphragm that a kind of copper nitride of embodiment according to the present invention is respectively adopted and is modified The asymmetrical cell charging and discharging curve figure of assembly；

Fig. 7 A is all charging and discharging curves of head using the lithium battery of unmodified diaphragm；

Fig. 7 B is filling in first week for the lithium battery for the diaphragm being modified using a kind of copper nitride of embodiment according to the present invention Discharge curve；

Fig. 8 A is the surface conductance performance test result of collector before modified；With

Fig. 8 B is the surface conductivity using the modified collector of copper nitride of a kind of embodiment according to the present invention It can test result.

Specific embodiment

The present invention is further described in detail With reference to embodiment, and the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.

Figure 1A and 1B respectively illustrates the structural schematic diagram of the modified membrane material of copper nitride and that copper nitride is modified The structural schematic diagram of grain material.As shown in Figure 1A and 1B, copper nitride can be with film on membrane material and granular material surface Form exist.In use, copper layer of nitride film (boundary layer) is used close to negative side.

Embodiment 1

The present embodiment is modified lithium anode piece using copper nitride.

1. being pre-processed first to metal lithium bands, scraped off with blade/scraping blade blunt with a thickness of 120 μm of metal lithium bands surface Change layer, then with sand paper or polishing rod sanding and polishing.Then by glove box rolling device, by the lithium band and punching copper of sanding and polishing Foil roll-in needs together, in nipping process in the front and back sides cladding thickness of lithium band to be 180 μm of PE film to prevent and roller bearing Adhesion, roll-in thickness are arranged at 400 μm, so obtain more smooth uniform lithium band.Obtained lithium band logical is crossed into glove box punching Equipment strikes outButton cell negative plate.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained negative electrode tab is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 1Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, sputtering power 40W, when sputtering Between be 20min.

Surface and section using the S8600 type scanning electronic microscope observation lithium anode purchased from Hitachi, Ltd, knot Fruit shows that metallic lithium surface forms uniform film layer, with a thickness of about 300nm.Using photoelectron spectroscopy (XPS) characterization film layer Composition, the chemical element metering ratio of copper nitrogen is 3:1 in film layer as the result is shown.

3. using the cyclicity of Li-Li Symmetrical cells modeling lithium anode.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, Unmodified negative electrode tab prepared by the middle copper nitride prepared respectively using step 2 modified lithium anode and step 1 is cathode, electricity The LiTFSI/DME-DOL (volume ratio of DME and DOL are 1:1) and lithium piece that the concentration that solution liquid is LiTFSI is 1M are anode.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius, as a result as shown in Figure 5.By Fig. 5 Cyclic curve can be seen that the polarization of the modified lithium anode of copper nitride and reduce, it can thus be appreciated that the SEI formed is more steady It is fixed.

Battery dismantle after by observing cathode of lithium surface respectively purchased from the S8600 type scanning electron microscope of Hitachi, Ltd, Comparison discovery Li dendrite is inhibited.

Embodiment 2

The present embodiment is modified lithium anode piece using copper nitride.

1. being handled in advance metal lithium bands first, scraped off with blade/scraping blade blunt with a thickness of 120 μm of metal lithium bands surface Change layer, then with sand paper or polishing rod sanding and polishing.Then the PE film for being 180 μm in the tow sides cladding thickness of metal lithium bands, It is cold-pressed, so obtains more smooth uniform lithium band.Obtained lithium band logical is crossed into glove box punching equipment, is struck outButton cell negative plate.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained negative electrode tab is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 2Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, sputtering power 50W, when sputtering Between be 30min.

Surface and section using the S8600 type scanning electronic microscope observation lithium anode purchased from Hitachi, Ltd, knot Fruit shows that metallic lithium surface forms uniform film layer, with a thickness of about 500nm.Using photoelectron spectroscopy (XPS) characterization film layer Composition, the chemical element metering ratio of copper nitrogen is 3:2 in film layer as the result is shown.

3. characterizing the cyclicity of lithium anode.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, Unmodified negative electrode tab prepared by the middle copper nitride prepared respectively using step 2 modified lithium anode and step 1 is cathode, electricity Solution liquid be LiTFSI concentration be 1M LiTFSI/DME-DOL (volume ratio of DME and DOL are 1:1) and LiFePO4 be Anode.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that circulation 500 weeks Afterwards, using the capacity residue 80% of the battery of the modified lithium anode of copper nitride, and it is unmodified negative to use step 1 to prepare The capacity residue 34% of pole piece, and substantially mentioned using all efficiency of the head of the battery of the modified lithium anode of copper nitride It rises.From cyclic curve as can be seen that the polarization for the lithium anode that copper nitride is modified reduces, it can thus be appreciated that the SEI formed is more Stablize.

Embodiment 3

The present embodiment is modified Cu collector using copper nitride.

1. pre-processed first to Cu foil surface, by with a thickness of 12 μm of copper foil in the surface exhibition of large area flat substrate It is flat, it is cleaned repeatedly with alcohol and deionized water, is dried 6 hours at 110 DEG C in vacuum drying oven, so obtain the Cu of clean surface Foil.Then, obtained Cu foil is struck out by punching equipmentButton cell negative plate.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained negative electrode tab is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 1Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, sputtering power 40W, when sputtering Between be 10min.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Metal copper foil surface forms uniform film layer, with a thickness of about 150nm.The composition of film layer is characterized using photoelectron spectroscopy (XPS), The chemical element metering ratio of copper nitrogen is 3:1 in film layer as the result is shown.

3. using Li-Cu battery mode characterization cycle efficieny and dendritic growth situation.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure, wherein unmodified cathode prepared by the cathode and step 1 that are modified respectively with copper nitride prepared by step 2, electrolyte The LiTFSI/DME-DOL (volume ratio of DME and DOL are 1:1) and lithium piece that concentration for LiTFSI is 1M are to electrode.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that modified cathode Cycle efficieny is stablized 99.5% or more, is recycled 600 weeks or more, and unmodified cathode is only able to maintain 280 weeks.

In addition, battery observes the table of copper electrode by the S8600 type scanning electron microscope purchased from Hitachi, Ltd after dismantling Face, as a result as shown in Fig. 3 A, 3B, 4A and 4B.

Fig. 3 A and 3B respectively illustrate the scanning electron microscopic picture of the modified cathode rear surface of charging of copper nitride and do not change Property cathode charge a rear surface scanning electron microscopic picture.The results show that compared to unmodified cathode, what copper nitride was modified Cathode inhibits the growth of Li dendrite.

Fig. 4 A and 4B respectively illustrate the scanning electron microscopic picture and copper nitride modification of unmodified cathode charge and discharge after a week Cathode charge and discharge scanning electron microscopic picture after a week.The results show that compared to unmodified cathode, the modified cathode of copper nitride Substantially exist without " dead lithium ".

Embodiment 4

The present embodiment is modified Cu collector using copper nitride.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained negative electrode tab is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 1Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, sputtering power 60W, when sputtering Between be 5min.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on metal copper foil surface, with a thickness of about 100nm.Using the group of photoelectron spectroscopy (XPS) characterization film layer At the chemical element metering of copper nitrogen becomes 3:1 than group in film layer as the result is shown.

Using the modified pole Cu of copper nitride of the 8 type atomic force microscope of Multimode purchased from Bruker company to preparation Piece and unmodified Cu pole piece carry out the performance test of surface conductance, as a result as shown in Figure 8 A and 8 B.Interpretation of result shows nitrogen Changing the modified Cu pole piece of copper, there is more uniform surface conductance to be distributed.It is not intended to be restricted by theory, it is believed that this is to Li dendrite Inhibition plays key effect.

3. characterizing its cycle efficieny and dendritic growth situation using Li-Cu battery mode.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, The modified Cu electrode of the middle copper nitride using preparation, LiTFSI/DME-DOL that the concentration that electrolyte is LiTFSI is 1M (DME and The volume ratio of DOL is 1:1) and lithium piece be to electrode.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Cu electrode have more excellent cyclical stability, cycle efficieny stablize 99.5% or more, can keep 700 weeks or more.

Battery is changed after dismantling by the copper nitride after the S8600 type scanning electron microscope observation circulation purchased from Hitachi, Ltd Property copper negative terminal surface, no dendrite generates, and Li dendrite is inhibited.

Embodiment 5

The present embodiment is modified Cu collector using copper nitride.

2. obtained pole piece is fixed on the sample carrier of electron beam evaporation, electricity is transferred to by nitrogen atmosphere protective device The main cabin of beamlet evaporation equipment, carries out nitridation plated copper film, and target chooses Ni metal target.Electron beam evaporation deposition total gas pressure is 1Pa, reaction gas choose N₂(10%), Ar (90%) is selected in carrier gas, and plated film rate control is in 0.5 angstrom/s, sputtering time 5min.Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on metal copper foil surface, with a thickness of about 150nm.Using the group of photoelectron spectroscopy (XPS) characterization film layer At the chemical element metering of copper nitrogen becomes 0.5:1 than group in film layer as the result is shown.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure, wherein the Cu electrode modified using the copper nitride of preparation, the LiTFSI/DME- that the concentration that electrolyte is LiTFSI is 1M DOL (volume ratio of DME and DOL are 1:1) and lithium piece are to electrode.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride was modified Cu electrode has more excellent cyclical stability, and cycle efficieny is stablized 99.5% or more, can be kept 550 weeks or more.

Embodiment 6

The present embodiment is modified Cu collector using copper nitride.

2. obtained pole piece is fixed on the sample carrier of electron beam evaporation, electricity is transferred to by nitrogen atmosphere protective device The main cabin of beamlet evaporation equipment, carries out nitridation plated copper film, and target chooses Ni metal target.Electron beam evaporation deposition total gas pressure is 2Pa, reaction gas choose N₂(75%), Ar (25%) is selected in carrier gas, and plated film rate control is in 1 angstrom/s, sputtering time 5min. Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on metal copper foil surface, with a thickness of about 300nm.Using the group of photoelectron spectroscopy (XPS) characterization film layer At the chemical element metering of copper nitrogen becomes 4:1 than group in film layer as the result is shown.

Embodiment 7

The present embodiment is modified diaphragm using copper nitride.

1. being pre-processed first to diaphragm.It will be washed into a thickness of 16 μm, the PP diaphragm that porosity is 45% Sequin, after in vacuum drying oven dry 24 hours at 60 DEG C, so obtain the PP diaphragm of free from admixture gas absorption.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained PP diaphragm is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 1Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, sputtering power 40W, when sputtering Between be 30min.The diaphragm of success plated film should not have fold, and sample is transferred quickly to glove box after the completion by plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on membrane surface, with a thickness of about 500nm.Using the composition of photoelectron spectroscopy (XPS) characterization film layer, knot Fruit shows that the chemical element metering of copper nitrogen in film layer becomes 3:1 than group.

3. using LiCoO₂The half-cell system of-Li characterizes its cycle efficieny.

The assembling of battery is carried out in drying room, specific battery uses CR2032 button cell structure, wherein there will be nitridation Battery is assembled towards cathode in the side of copper coating, and lithium piece is cathode, LiCoO₂For anode, electrolyte is LiPF₆Concentration is 1M's LiPF₆/ EC-DMC (volume ratio of EC and DMC are 1:1).In addition, using the assembly CR2032 button electricity of PP diaphragm made from step 1 Pond is as a comparison case.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.

Fig. 6 shows the asymmetrical cell charging and discharging curve using the modified diaphragm of copper nitride and the assembly of unmodified diaphragm Figure.The results show that the diaphragm circulation that copper nitride is modified is more stable, 99% or more holding of coulombic efficiency did not changed more than 500 weeks The diaphragm of property is only able to maintain 300 weeks or so.

Fig. 7 A and 7B respectively illustrate filling in first week for the lithium battery for the diaphragm being modified using unmodified diaphragm and copper nitride Discharge curve.The results show that all cycle efficienies of head of battery can be substantially improved in modified diaphragm, it is so macrocyclic capacity Holding is laid a solid foundation.

Using purchased from Germany Zahner IM6 type impedance spectrum tester to using modification diaphragm and step 1 made from not The battery of modified diaphragm carries out impedance spectrum test.The results show that the impedance magnitude of modified diaphragm is significantly lower than unmodified Diaphragm.

Battery observes the cathode of lithium table after circulation by the S8600 type scanning electron microscope purchased from Hitachi, Ltd after dismantling Face, no dendrite generate, and Li dendrite is inhibited.

Embodiment 8

The present embodiment is modified diaphragm using copper nitride.

2. being transferred to magnetic by nitrogen atmosphere protective device during the sample that obtained PP diaphragm is fixed on magnetron sputtering is dragged The transfer chamber for controlling sputtering equipment is transferred to main cabin later, carries out copper nitride sputter coating, and target chooses Ni metal target.Magnetic control splashes Penetrating plated film total gas pressure is 1Pa, and reaction gas chooses N₂(60%), Ar (40%) is selected in carrier gas, sputtering power 60W, when sputtering Between be 10min.The diaphragm of success plated film should not have fold, and sample is transferred quickly to glove box after the completion by plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on membrane surface, with a thickness of about 400nm.Using the composition of photoelectron spectroscopy (XPS) characterization film layer, knot Fruit shows that the chemical element metering of copper nitrogen in film layer becomes 3:1 than group.

3. using LiCoO₂The half-cell system of-Li characterizes its cycle efficieny.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Diaphragm circulation it is more stable, coulombic efficiency is kept 99% or more more than 500 weeks.

Battery is negative by the lithium after the S8600 type scanning electron microscope observation head Zhou Xunhuan purchased from Hitachi, Ltd after dismantling Pole surface, no dendrite generate, and Li dendrite is inhibited.

Embodiment 9

The present embodiment is modified diaphragm using copper nitride.

2. being transferred to electricity by nitrogen atmosphere protective device during the sample that obtained PP diaphragm is fixed on magnetron sputtering is dragged The main cabin of beamlet evaporation equipment carries out nitridation plated copper film, and target chooses Ni metal target, using rotary plated film mode.Electronics Beam evaporation plated film total gas pressure is 1Pa, and reaction gas chooses N₂Ar (0.5Pa) is selected in (0.5Pa), carrier gas, and plated film rate control is 1 Angstrom/s, sputtering time 30min.Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on membrane surface, with a thickness of about 400nm.Using the composition of photoelectron spectroscopy (XPS) characterization film layer, knot Fruit shows that the chemical element metering of copper nitrogen in film layer becomes 3:2 than group.

3. using LiCoO₂The half-cell system of-Li characterizes its cycle efficieny.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, Middle to have the side of nitridation copper coating to assemble battery towards cathode, lithium piece is cathode, LiCoO₂For anode, electrolyte is LiPF₆It is dense Degree is the LiPF of 1M₆/ EC-DMC (volume ratio of EC and DMC are 1:1).

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Diaphragm circulation it is more stable, coulombic efficiency is kept 98.5% or more more than 600 weeks.

Embodiment 10

The present embodiment is modified diaphragm using copper nitride.

2. being transferred to electricity by nitrogen atmosphere protective device during the sample that obtained PP diaphragm is fixed on magnetron sputtering is dragged The main cabin of beamlet evaporation equipment carries out nitridation plated copper film, and target chooses Ni metal target, using rotary plated film mode.Electronics Beam evaporation plated film total gas pressure is 1Pa, and reaction gas chooses N₂Ar (0.5Pa) is selected in (0.5Pa), carrier gas, and plated film rate control exists 0.5 angstrom/s, sputtering time 40min.Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Uniform film layer is formd on membrane surface, with a thickness of about 200nm.Using the composition of photoelectron spectroscopy (XPS) characterization film layer, knot Fruit shows that the chemical element metering of copper nitrogen in film layer becomes 3:1 than group.

3. using LiCoO₂The half-cell system of-Li characterizes its cycle efficieny.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Diaphragm circulation it is more stable, coulombic efficiency is kept 99.5% or more more than 500 weeks.

Do not changed using the IM6 type impedance spectrum tester purchased from Germany Zahner to using made from modified diaphragm and step 1 Property diaphragm battery carry out impedance spectrum test.The results show that the impedance magnitude of modified diaphragm is significantly lower than unmodified diaphragm.

Embodiment 11

The present embodiment is modified diaphragm using copper nitride.

2. on the coating machine that obtained PP diaphragm is fixed in drying room, nitridation copper powders to be tuned into the slurry of appropriate viscosity Material, wherein slurry is made of base-material and aqueous solvent, and base-material proportion is 40 weight %, and solvent proportion is 60 weight %, Base-material by nitridation copper powders, the Kynoar adhesive purchased from AlFa, purchased from the polyethylene glycol dispersing agent of Sigma company and purchase It is formed from the polyoxyethylene aliphatic alcohol ether wetting agent of Sigma company, wherein the partial size D50 of nitridation copper powders is 0.1 μm, in base-material In accounting be 92.5 weight %, wetting agent and the adhesive accounting in base-material are respectively 2.5 weight %, and dispersing agent accounts in base-material Than for 2.5 weight %.Sample after coating is transferred to vacuum drying oven, it is 24 hours dry at 70 DEG C, it then takes out and turns rapidly Glove box is moved to, is washed intoSequin, it is dry after coating layer thickness be 0.9 μm.

3. using LiCoO₂The half-cell system of-Li characterizes coulombic efficiency, the properties such as high rate performance and polarization.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, Middle to have the side of nitridation copper coating to assemble battery towards cathode, lithium piece is cathode, LiCoO₂For anode, electrolyte is LiPF₆It is dense Degree is the LiPF of 1M₆/ EC-DMC (volume ratio of EC and DMC are 1:1).In addition, being assembled using PP diaphragm made from step 1 CR2032 button cell is as a comparison case.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Diaphragm cycle performance be substantially improved, capacity residue 83% after 500 weeks.

Embodiment 12

The present embodiment is modified diaphragm using copper nitride.

1. being pre-processed first to diaphragm.It will be washed into a thickness of 20 μm, the PP diaphragm that porosity is 45% Sequin, after in vacuum drying oven dry 24 hours at 60 DEG C, so obtain the PP diaphragm of free from admixture gas absorption.

2. on the coating machine that obtained PP diaphragm is fixed in drying room, nitridation copper powders to be tuned into the slurry of appropriate viscosity Material, wherein slurry is made of base-material and aqueous solvent, and base-material proportion is 40 weight %, and solvent proportion is 60 weight %, Base-material by nitridation copper powders, the Kynoar adhesive purchased from AlFa, purchased from the polyethylene glycol dispersing agent of Sigma company and purchase It is formed from the polyoxyethylene aliphatic alcohol ether wetting agent of Sigma company, wherein the partial size D50 of nitridation copper powders is 0.05 μm, in base Accounting in material is 95 weight %, and wetting agent accounting in base-material is 2 weight %, and adhesive accounting in base-material is 1.5 weights % is measured, dispersing agent accounting in base-material is 1.5 weight %.Sample after coating is transferred to vacuum drying oven, it is dry at 70 DEG C It 24 hours, then takes out and is transferred quickly to glove box, be washed intoSequin, after coating is dry with a thickness of 0.5 μm.

3. using LiCoO₂The properties such as half-cell system characterization coulombic efficiency, high rate performance and the polarization of-Li.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that copper nitride is modified Diaphragm cycle performance be substantially improved, capacity residue 82% after 550 weeks.

Embodiment 13

The present embodiment is modified cathode particle hard carbon powder using copper nitride.

1. firstly, under nitrogen protection, the hard carbon powder that partial size D50 is 15 μm being removed magnetic impurity, is mixed into methoxyl group It is stirred in the mixed solution of copper and benzylamine, methoxyl group copper mass is 0.5g, benzylamine 20ml in mixed solution.Then it is protected in nitrogen Under shield, constant temperature stirs 20min at 110 DEG C, and natural cooling keeps continuous stirring in cooling procedure.N-hexane is used after cooling Cleaning three times, filters, and dry in nitrogen stream, obtains cathode dusty material.Wherein, copper nitride stoichiometrically calculates, Weight percent of the copper nitride in cathode dusty material is 1%.

Using the S8600 type scanning electronic microscope observation cathode dusty material for being purchased from Hitachi, Ltd.The results show that hard The particle that partial size is 100nm is coated on carbon particle surface.

Using the composition using photoelectron spectroscopy (XPS) characterization coating particles, the chemistry of copper nitrogen is first in particle as the result is shown Element metering becomes 3:1 than group.

2. the slurry that obtained cathode dusty material is tuned into appropriate viscosity is carried out smear, wherein slurry is by base-material and solvent Water composition, base-material proportion are 40 weight %, and solvent proportion is 60 weight %, and collector is Cu foil.Preliminarily dried, punching Piece claims piece, then dries piece at 110 DEG C, and cathode pole piece is made, and taking-up is transferred quickly to glove box.

3. using LiCoO₂The properties such as full battery system cycle performance, high rate performance and polarization.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, adopts With the cathode pole piece of preparation, electrolyte is LiPF₆Concentration is the LiPF of 1M₆/ EC-DMC (volume ratio of EC and DMC are 1:1), LiCoO₂For anode.In addition, using the unmodified partial size D50 for removing magnetic impurity for the hard carbon powder of 5.5um, according to step 2 methods prepare cathode pole piece, are then assembled into CR2032 button cell as a comparison case.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that being changed using copper nitride Property hard carbon be negative electrode material battery cycle performance, high rate performance and polarization property and use unmodified hard carbon for cathode The battery of material is compared, and is significantly improved.Specifically, the hard carbon for using copper nitride modified is the battery of negative electrode material, and 82.4% Up to 550 weeks or more under the conditions of capacity retention ratio, polarization is reduced to 0.06V from 0.12V.

Using the IM6 type impedance spectrum tester purchased from Germany Zahner to the hard carbon modified using copper nitride of circulation front and back For negative electrode material battery and use unmodified hard carbon for negative electrode material battery carry out impedance spectrum test.The results show that adopting It is substantially reduced with the impedance for the cathode pole piece that the modified hard carbon of copper nitride is negative electrode material.

It is believed that the hard carbon particle for being coated with copper nitride can in its surface in situ generate while have electronic conductance and from The hybrid conductive network layer of sub- conductance, and then greatly contained the side reaction on hard carbon surface, and be coated with the hard of copper nitride Carbon particle also has better high rate performance.In addition, the electronic conductance due to hard carbon in embedding full lithium rear surface still can induce The deposition of lithium ion fills up hard carbon void among particles, so forms lithium carbon composite electrode in situ, can greatly promote hard carbon The capacity of cathode itself, and original cycle life can be kept.

Embodiment 14

The present embodiment is modified cathode granular graphite using copper nitride.

1. firstly, under nitrogen protection, the graphite that partial size D50 is 5.5 μm being removed magnetic impurity, is mixed into phenyl copper, benzene It is stirred in the mixed solution of amine and acetone, phenyl copper mass is 0.5g in mixed solution, and benzylamine is 20ml and acetone is 50ml. Then under nitrogen protection, constant temperature stirs 0.5h at 150 DEG C, and natural cooling keeps continuous stirring in cooling procedure.It is cooling It is cleaned three times with ethyl alcohol, filtering, and is dried in nitrogen stream afterwards, obtain cathode dusty material.Wherein, copper nitride is stoichiometrically Than calculating, weight percent of the copper nitride in cathode dusty material is 0.05%.

Using the S8600 type scanning electronic microscope observation cathode dusty material for being purchased from Hitachi, Ltd.The results show that in stone The particle that partial size is 100nm is coated on the surface of ink powder end.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, adopts With the cathode pole piece of preparation, electrolyte is LiPF₆Concentration is the LiPF of 1M₆/ EC-DMC, LiCoO₂For anode.In addition, using removing The hard carbon powder that the unmodified D50 partial size of magnetic impurity is 5.5um is removed, cathode pole piece is prepared according to step 2 method, then group Dress up CR2032 button cell as a comparison case.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that being changed using copper nitride Property graphite be negative electrode material battery cycle performance, high rate performance and polarization property and use unmodified graphite for cathode The battery of material is compared, and is significantly improved.Specifically, for the battery of negative electrode material, 80% holds the graphite for using copper nitride modified Up to 700 weeks or more under the conditions of amount conservation rate, polarization is reduced to 0.06V from 0.12V.

Using the IM6 type impedance spectrum tester purchased from Germany Zahner to the graphite modified using copper nitride of circulation front and back For negative electrode material battery and use unmodified graphite for negative electrode material battery carry out impedance spectrum test.The results show that adopting It is substantially reduced with the impedance for the cathode pole piece that the modified graphite of copper nitride is negative electrode material.

It is believed that the graphite particle for being coated with copper nitride can in its surface in situ generate while have electronic conductance and from The hybrid conductive network layer of sub- conductance, and then greatly contained the side reaction of graphite surface, and be coated with the stone of copper nitride Ink powder end also has better high rate performance.In addition, the electronic conductance due to graphite in embedding full lithium rear surface still can induce The deposition of lithium ion fills up the gap between graphite particle, so forms lithium carbon composite electrode in situ, can greatly promote graphite The capacity of cathode itself, and original cycle life can be kept.

Embodiment 15

The present embodiment is using copper nitride to inorganic solid electrolyte Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP) piece is modified.

1. being sintered 8 hours by inorganic solid electrolyte LAGP tabletting, and at 1100 DEG C, its conductivity is set to reach its optimal Value.

2. nitridation copper powders, binder SBR and aqueous solvent that partial size is 0.1 μm to be tuned into the slurry of appropriate viscosity, in step The electrolyte sheet surface of rapid 1 preparation carries out spin coating.Sample after coating is transferred in vacuum drying oven, dry 24 at 110 DEG C Hour, the modified electrolyte sheet of copper nitride is obtained, taking-up is transferred quickly to glove box.Wherein, the ratio of copper nitride is in coating 95 weight %, the ratio of binder are 5 weight %, and coating layer thickness is 1.3 μm after drying.

3. the Symmetrical cells system using Li-Li characterizes the properties such as its cycle performance, high rate performance and polarization.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure.Tool Body, use lithium piece for cathode and to electrode, the electrolyte sheet and step 1 that copper nitride modification is respectively adopted prepare unmodified Electrolyte sheet, and will there is the side of nitridation copper coating to assemble battery towards cathode.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.2C multiplying power, and test temperature is 60 degrees Celsius.The results show that with using unmodified The battery of electrolyte sheet compare, substantially reduced using the polarization of the battery of the modified electrolyte sheet of copper nitride, cycle life is big It is big to be promoted.

Embodiment 16

The present embodiment is using copper nitride to inorganic solid electrolyte Li_1.3Al_0.3Ti_1.7(PO₄)₃(LATP) piece is modified.

1. being sintered 8 hours by inorganic solid electrolyte LATP tabletting, and at 1100 DEG C, its conductivity is set to reach its optimal Value.

2. the sample that inorganic solid electrolyte piece is fixed on electron beam evaporation made from step 1 is dragged, pass through nitrogen gas Atmosphere protective device is transferred to the main cabin of electron beam evaporation equipment, carries out nitridation plated copper film, and target chooses Ni metal target.Electron beam Evaporation coating total gas pressure is 1Pa, and reaction gas chooses N₂Ar (ratio 50%) is selected in (ratio 50%), carrier gas, plated film speed Rate is controlled in 1 angstrom/s, plated film time 5min.Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation solid electrolyte sheet purchased from Hitachi, Ltd, Solid electrolyte sheet surface forms uniform film layer as the result is shown, with a thickness of about 280nm.Using photoelectron spectroscopy (XPS) table The composition of film layer is levied, the chemical element metering of copper nitrogen becomes 3:1 than group in film layer as the result is shown.

3. properties such as Symmetrical cells system characterization cycle performance, high rate performance and polarization using Li-Li.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure.Specifically, it uses lithium piece for cathode and to electrode, the modified solid electrolyte sheet of copper nitride and step 1 is respectively adopted The unmodified solid electrolyte sheet of preparation, and will there is the side of nitridation copper coating to assemble battery towards cathode.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.2C multiplying power, and test temperature is 60 degrees Celsius.The results show that with using unmodified The battery of solid electrolyte sheet compare, substantially reduced, followed using the polarization of the battery of the modified solid electrolyte sheet of copper nitride The ring service life greatly promotes.

Embodiment 17

2. the sample that inorganic solid electrolyte piece is fixed on magnetron sputtering made from step 1 is dragged, pass through nitrogen atmosphere Protective device is transferred to the main cabin of magnetron sputtering apparatus to the transfer chamber of magnetron sputtering apparatus, is transferred to main cabin later, carries out Plated copper film is nitrogenized, target chooses Ni metal target.Magnetron sputtering total gas pressure is 1Pa, and reaction gas chooses N₂(70%), carrier gas is selected Ar (30%), plated film power are 30W, plated film time 30min.Sample is transferred quickly to glove box after the completion of plated film.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure.Specifically, it uses lithium piece for cathode and to electrode, the modified solid electrolyte sheet of copper nitride and step 1 is respectively adopted The non-modified solid electrolyte sheet of preparation, and will there is the side of nitridation copper coating to assemble battery towards cathode.

Embodiment 18

The present embodiment is modified polyethylene glycol oxide solid electrolyte using copper nitride.

1. weighing 2 grams of double trifluoromethanesulfonimide lithiums (LiTFSI), the copper nitride particle that 1 gram particle diameter is 0.1 μm first With 30 milliliters of acetonitrile solvents, ultrasound at least 15 minutes is placed in same container to being completely dispersed.Then 10 grams are weighed purchased from Sigma Polyethylene glycol oxide (PEO) be dissolved in and having dispersed in solution, stir 6 hours, wherein the oxygen atom of PEO polymer and lithium salts and lithium are former Son is maintained at 20:1 than range.The solution stirred evenly is coated on surface of silicon, is dried at 50 DEG C, is prepared into suitable big Small, removing obtains with a thickness of 30 μm, porosity being the modified polyoxyethylene solid electrolyte piece of 10% copper nitride, spare.

2. properties such as Symmetrical cells system characterization cycle performance, high rate performance and polarization using Li-Li.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure, wherein using lithium piece for cathode and to electrode, using the modified polyethylene oxide base solid electrolyte piece of copper nitride.Separately Outside, other than not adding copper nitride, unmodified polyoxyethylene solid electrolyte piece, and group are prepared according to the method for step 1 Dress up CR2032 button cell as a comparison case.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 55 degrees Celsius.The results show that with using unmodified The battery of polyoxyethylene solid electrolyte sheet compare, using the battery of the modified polyethylene glycol oxide solid electrolyte sheet of copper nitride Polarization substantially reduce, cycle life improves 1.5 times.

Embodiment 19

The present embodiment is modified polyacrylonitrile solid electrolyte using copper nitride.

1. weighing 1 gram of double trifluoromethanesulfonimide lithium (LiTFSI), the copper nitride nanometer that 2 gram particle diameters are 100nm first Particle, the aluminum oxide nanoparticle and 20 milliliters of acetonitrile solvents that 0.2 gram particle diameter is 50nm, are placed in ultrasound at least 15 in same container Minute to being completely dispersed.Then 10 grams of commercial polypropylene nitriles (PAN) purchased from Sigma are weighed and are dissolved in and have been dispersed in solution, stirring 6 Hour, wherein the oxygen lithium of PAN polymer and lithium salts is maintained at 20:1 than range.The solution stirred evenly is coated on silicon substrate table Face is dried at 50 DEG C, is prepared into suitable size, and removing obtains being modified with a thickness of 60 μm, the copper nitride that porosity is 0% poly- Acrylonitrile solid electrolyte piece, it is spare.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 55 degrees Celsius.The results show that with using unmodified The battery of polyacrylonitrile solid electrolyte sheet compare, using the battery of copper nitride modified polyacrylonitrile solid electrolyte sheet Polarization substantially reduces, and cycle life improves 2 times.

Embodiment 20

The present embodiment is modified polyimides solid electrolyte using copper nitride.

1. weighing 0.5 gram of double trifluoromethanesulfonimide lithium (LiTFSI) and 5 milliliters of acetonitrile solvents first, it is placed in same appearance In device ultrasound at least 15 minutes to being completely dispersed.Then weigh 10 grams of polyimides (PI) purchased from Sigma be dissolved in dispersed it is molten In liquid, stir 6 hours, wherein the oxygen lithium of PI polymer and lithium salts is maintained at 20:1 than range.The solution stirred evenly is coated It in surface of silicon, is dried at 50 DEG C, is prepared into suitable size, removing obtains with a thickness of 60 μm, the nitrogen that porosity is 10% Change the modified polyimides solid electrolyte piece of copper, it is spare.

2. being protected during the sample that obtained polyimides solid electrolyte piece is fixed on magnetron sputtering is dragged by nitrogen atmosphere Protection unit is transferred to the transfer chamber of magnetron sputtering apparatus, is transferred to main cabin later, carries out nitridation plated copper film, and target chooses Ni metal Target.Magnetron sputtering total gas pressure is 1Pa, and reaction gas chooses N₂(50%), Ar (50%) is selected in carrier gas, and plated film power is 40W, plating The film time is 15min.Sample is transferred quickly to glove box after the completion of plated film.

Surface and section using the S8600 type scanning electronic microscope observation cathode purchased from Hitachi, Ltd, as the result is shown Solid electrolyte surface forms uniform film layer, with a thickness of about 100nm.Using the group of photoelectron spectroscopy (XPS) characterization film layer At the chemical element metering of copper nitrogen becomes 3:1 than group in film layer as the result is shown.

The assembling of battery is carried out in the glove box of argon gas protection or in drying room, specific battery uses CR2032 button electricity Pool structure.Specifically, it uses lithium piece for cathode and to electrode, the modified polyimides solid electrolyte piece of copper nitride is respectively adopted The unmodified polyimides solid electrolyte piece prepared with step 1, and will there is the side of nitridation copper coating to fill towards cathode With battery.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 50 degrees Celsius.The results show that with using unmodified The battery of polyimides solid electrolyte piece compare, using the battery of copper nitride modified polyimides solid electrolyte piece Polarization substantially reduces, and cycle life was promoted to 350 weeks by 80 weeks.

Embodiment 21~41

In embodiment 21~41, using component shown by table 1, CR2032 button is assembled in the glove box of argon gas protection Battery, septation and electrolyte sheet have the side of nitridation copper coating towards cathode, and the composition of battery is shown in Table 2.

Table 1

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.Battery dismantle after by purchased from day Cathode of lithium surface Li dendrite after the S8600 type scanning electron microscope observation circulation of vertical company generates situation.The result of test It is shown in Table 2.

Table 2

Comparative example 1

Comparative example 1 is modified diaphragm using inorganic filler.

2. obtained diaphragm is fixed on the coating machine in drying room, by inorganic filler Al₂O₃It is tuned into the slurry of appropriate viscosity Material coating diaphragm, the Al that slurry is 100 nanometers by average grain diameter₂O₃It is formed with binder SBR, inorganic filler Al in slurry₂O₃Institute Accounting example is 50 weight %, and the ratio of binder SBR is 1 weight %.Sample after coating is transferred to vacuum drying oven, 70 DEG C of bakings 24 hours, for the coat after drying with a thickness of 2 μm, rear take out was transferred quickly to glove box, was washed intoSequin.

3. using LiCoO₂The half-cell system of-Li characterizes its cycle performance.

The assembling of battery is carried out in drying room, specific battery uses CR2032 button cell structure, wherein will have inorganic Battery is assembled towards cathode in the side of filler coat, and lithium piece is cathode, LiCoO₂For anode, electrolyte is LiPF₆Concentration is 1M LiPF₆/ EC-DMC (volume ratio of EC and DMC are 1:1).In addition, assembling CR2032 button using PP diaphragm made from step 1 Battery is as reference.

Assembled battery is enterprising in Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Row test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.As the result is shown 80% capacity Under conservation rate, circulation was promoted to 500 weeks by original 350 weeks.

Battery observes the cathode of lithium table after circulation by the S8600 type scanning electron microscope purchased from Hitachi, Ltd after dismantling , still there is dendrite generation in face, and Li dendrite is not inhibited substantially effectively.

Comparative example 2

1. being modified using graphene to graphite particle.

(1) graphite that partial size D50 is 5.5 μm is removed into magnetic impurity, then ultrasonic disperse obtains stone in etoh solvent Black suspension, the weight fraction of graphite is 10% in graphite suspension；

(2) by graphite oxide ultrasonic dissolution in etoh solvent, graphene oxide solution is obtained, in graphene oxide solution The weight fraction of graphite oxide is 5%；

(3) it is 0.1:1 by the mass ratio of graphene oxide and graphite, graphite suspension is added in graphene oxide solution, Ultrasound mixes, and then removes solvent, obtains dry solid powder；

(4) in a nitrogen atmosphere, step (3) resulting solid powder is handled at 800 DEG C 3h, cooled down to get stone is arrived The graphite negative material of lithium ion battery of black alkene cladding.

2. the slurry that the graphite negative material of lithium ion battery of obtained graphene coated is tuned into appropriate viscosity is applied Piece, wherein slurry is made of base-material and aqueous solvent, and base-material proportion is 40 weight %, and solvent proportion is 60 weight %, Collector is Cu foil.Preliminarily dried, punching claim piece, then dry piece at 110 DEG C, and cathode pole piece is made, and taking-up is transferred quickly to Glove box.

3. using LiCoO₂Full battery system cycle performance.

The assembling of battery is carried out in the glove box of argon gas protection, specific battery uses CR2032 button cell structure, adopts With the cathode pole piece of preparation, electrolyte is LiPF₆Concentration is the LiPF of 1M₆/ EC-DMC, LiCoO₂For anode.

Battery is assembled to carry out on Wuhan indigo plant electrical measurement test system (LANHE, Wuhan Land Electronic Co., Ltd.) Test, carries out loop test to battery under 0.5C multiplying power, and test temperature is 30 degrees Celsius.The results show that first charge discharge efficiency reaches 90%, up to 400 weeks under the conditions of 80% capacity retention ratio.

Above-described specific embodiment has carried out further the purpose of the application, technical scheme and beneficial effects It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely the specific embodiment of the application Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include Within protection scope of the present invention.

Claims

1. a kind of modified lithium battery material of copper nitride, the lithium battery material includes lithium battery basic material and is coated on institute The copper nitride in lithium battery base material surface or the incorporation lithium battery basic material is stated, wherein the change of the copper nitride Formula is Cu_AN, wherein 0.5≤A≤4.

2. lithium battery material according to claim 1, wherein the lithium battery basic material is selected from negative electrode tab, afflux One of body, diaphragm, solid electrolyte sheet, negative electrode active material particle and inorganic solid electrolyte particle are a variety of, described Copper nitride is coated on the surface of the lithium battery basic material；Preferably, the copper being coated on the lithium battery basic material The thickness or particle size range of nitride are 1nm~30 μm；Or

The lithium battery basic material is copolymer solid electrolyte, and the copper nitride mixes the copolymer solid electrolyte In；Preferably, in terms of the weight of the lithium battery material, the incorporation of the copper nitride is 5~30 weight %, preferably 7 ~15 weight %.

3. lithium battery material according to claim 1 or 2, wherein 1≤A≤4, it is highly preferred that 1.5≤A≤3；

Preferably, the lithium battery basic material be selected from one of negative electrode tab, collector, diaphragm and solid electrolyte sheet or It is a variety of；It is highly preferred that the thickness or particle size range of the copper nitride being coated on the lithium battery basic material are the μ of 2nm~10 M, preferably 20nm~2 μm, more preferably 100nm~1.5 μm.

4. lithium battery material according to claim 2 or 3, wherein the negative electrode tab is lithium anode piece, composition metal Lithium cathode sheet or lithium alloy negative electrode tab；It is highly preferred that the lithium alloy negative electrode tab is lithium boron alloy negative electrode tab, lithium-aluminium alloy cathode Piece or lithium magnesium alloy negative electrode tab；

Preferably, the collector is copper foil, punching copper mesh, foam copper, nickel foil, punching nickel screen or nickel foam；It is highly preferred that institute State collector with a thickness of 3 μm~5mm, preferably 5~50 μm, such as 12 μm；

Preferably, the diaphragm is monolayer polyethylene diaphragm, single-layer polypropylene seperation film, three layers of polyethylene-polypropylene-polyethylene every Film, polyimide diaphragm, poly- aramid fiber diaphragm, cellulosic separator or polyetherimide diaphragm；

It is highly preferred that the diaphragm with a thickness of 10~50 μm, preferably 15~20 μm；Porosity is 10~50%, preferably 30~45%；

Preferably, the solid electrolyte sheet is inorganic solid electrolyte piece or copolymer solid electrolyte piece；

It is highly preferred that the inorganic solid electrolyte piece is by selected from one of following inorganic solid electrolyte or a variety of shapes At: Li₅La₃Ta₂O₁₂、Li₅La₃Nb₂O₁₂、Li₇La₃Sn₂O₁₂、Li_1+xAl_xGe_2-x(PO₄)₃、Li_3yLa_2/3-yTiO₃、LiZr_2-zTi_z (PO₄)₃、Li_1+mAl_mTi_2-m(PO₄)₃、Li_4-nGe_1-nP_nS₄, LiPON electrolyte, Li_3+pSi_pP_pO₄、Li₇La₃Zr₂O₁₂、Li_7- _qLa₃Zr_2-qTa_qO₁₂And Li₂S-P₂S₅System sulfide electrolyte；Wherein, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤ 2,0≤n≤1,0≤p≤2,0≤q≤1；

It is highly preferred that the polymer dielectric piece includes polymer dielectric and electrolytic salt；It is further preferred that described poly- Polymer electrolyte is selected from polyethylene glycol oxide, polyphenylene oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl acetate, gathers Methyl methacrylate, polyimides, poly- (vinylidene fluoride-hexafluoropropene), polyvinylpyrrolidone, poly- divinyl sulfide and One of polyethyleneglycol diacrylate is a variety of；It is further preferred that the electrolytic salt is selected from LiPF₆, double trifluoros Sulfonyl methane imine lithium, double fluorine sulfimide lithiums, LiNO₃、Li₂CO₃、LiF、LiBF₄, di-oxalate lithium borate, difluoro oxalate boric acid Lithium, LiSO₃CF₃, (fluorine sulphonyl) (positive perfluoro butyl sulphonyl) imine lithium and LiClO₄One of or it is a variety of；

It is highly preferred that the polymer dielectric piece with a thickness of 30~60 μm and porosity be 0~70%, preferably 0~ 10%.

5. lithium battery material according to claim 1 or 2, wherein the negative electrode active material particle is negative selected from silicon substrate Pole active material particle, carbon based negative electrodes active material particle, tin base cathode active material particle, stratiform negative electrode active material particle With one of organic compound negative electrode active material particle or a variety of；

Preferably, the negative electrode active material particle be selected from silicon-carbon cathode active material particle, silicon oxygen carbon activity material granule, Artificial graphite, natural graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, metallic tin, stannic oxide, lithium titanate, molybdenum disulfide and Li₂C₈H₄O₄One of or it is a variety of；

Preferably, the inorganic solid electrolyte particle is selected from Li₅La₃Ta₂O₁₂、Li₅La₃Nb₂O₁₂、Li₇La₃Sn₂O₁₂、Li₁₊ _xAl_xGe_2-x(PO₄)₃、Li_3yLa_2/3-yTiO₃、LiZr_2-zTi_z(PO₄)₃、Li_1+mAl_mTi_2-m(PO₄)₃、Li_4-nGe_1-nP_nS₄, lithium phosphorus oxygen Nitrogen electrolyte, Li_3+pSi_pP_pO₄、Li₇La₃Zr₂O₁₂、Li_7-qLa₃Zr_2-qTa_qO₁₂And Li₂S-P₂S₅In system sulfide electrolyte It is one or more；Wherein, 0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0≤n≤1,0≤p≤2,0≤q≤1；

Preferably, in terms of the weight of the lithium battery material, the covering amount of the copper nitride is 0.02~2 weight %, preferably For 0.05~1 weight %；

Preferably, the partial size D50 of the negative electrode active material particle is 2~20 μm, preferably 5~15 μm；Preferably, copper nitrogenizes The partial size of object is 20nm~2 μm, preferably 100~500nm.

6. the method for preparing lithium battery material described in any one of claims 1 to 5, the described method comprises the following steps:

(1) by vapor phase method, liquid phase method, solid phase method, cladding process, spray drying, electrostatic spinning or 3D printing in the lithium battery Coated copper nitride on basic material: or

(2) copper nitride is mixed into the lithium battery and mixing copper nitride with the component of the lithium battery basic material Basic material.

7. according to the method described in claim 6, wherein, the vapor phase method is magnetron sputtering, electron beam evaporation, thermal evaporation, original Sublayer deposition, pulsed laser deposition, chemical vapor deposition or plasma enhanced chemical vapor deposition；

Preferably, the liquid phase method is hydrothermal/solvent thermal method, complexed-precipitation method, coprecipitation, sol-gal process or melt growth Method；

Preferably, the solid phase method is powder solid phase method, combustion method or machine-alloying.

8. a kind of lithium battery, the lithium battery includes lithium battery material described at least one any one of claims 1 to 5.

9. lithium battery according to claim 8, the lithium battery also includes positive electrode, and the positive electrode is preferably phosphorus Sour iron lithium, cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt aluminium lithium, nickel ion doped, Li₂MnO₃、MnO₂、FeS₂、FeF₃、S、H₂O、 CO₂Or O₂。

10. chemical formula is Cu_AThe copper nitride of N is inhibiting lithium battery especially cathode of lithium battery surface Li dendrite formation and/or is mentioning Application in high lithium battery cycle performance, wherein 0.2≤A≤4, it is preferable that 0.5≤A≤4, it is highly preferred that 1≤A≤4, into one It walks preferably, 1.5≤A≤3.