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WO2023056635A1 - Matériau d'électrode positive pour batterie lithium-ion, son procédé de préparation et son application - Google Patents

Matériau d'électrode positive pour batterie lithium-ion, son procédé de préparation et son application Download PDF

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WO2023056635A1
WO2023056635A1 PCT/CN2021/122866 CN2021122866W WO2023056635A1 WO 2023056635 A1 WO2023056635 A1 WO 2023056635A1 CN 2021122866 W CN2021122866 W CN 2021122866W WO 2023056635 A1 WO2023056635 A1 WO 2023056635A1
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lithium
ion battery
positive electrode
doped
electrode material
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潘锋
赵庆贺
易浩聪
任恒宇
林海
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of battery positive electrode materials, in particular to a lithium ion battery positive electrode material and its preparation method and application.
  • Inorganic positive electrode materials include layered transition metal oxides represented by LiCoO 2 , LiNiO 2 , LiMnO 2 , etc., spinel structure materials represented by LiMn 2 O 4 and olivine represented by LiFePO 4 Oxide is a relatively mature material system for industrial applications.
  • LiCoO 2 LiCoO 2
  • LiNiO 2 LiNiO 2
  • LiMnO 2 etc.
  • spinel structure materials represented by LiMn 2 O 4
  • olivine represented by LiFePO 4 Oxide is a relatively mature material system for industrial applications.
  • the inorganic layered structure type material system occupies most of the lithium-ion battery market, but the application characteristics of different layered cathode material systems are not the same.
  • the advantages of LiCoO 2 material product maturity and stable performance make it widely used in the field of 3C electronic products; ternary layered materials, including NMC, NCA, etc., are widely used in the field of power batteries such as electric vehicles.
  • ternary layered materials including NMC, NCA, etc.
  • the charging voltage of LiCoO 2 material did not exceed 4.2V vs.
  • LiCoO2 material has the problems of fast capacity decay rate and low rate performance, which is related to the decomposition of electrolyte, the collapse of electrode material structure and the loss of oxygen in the lattice, and the CEI at the electrode material/electrolyte interface. It is closely related to the rapid accumulation of film layers. At the same time, for ternary layered materials, including NMC, NCA, etc., similar problems also exist under high voltage.
  • Coating treatment can not only stabilize the material structure, optimize the material morphology and improve the interface, and facilitate the interfacial ion transport process, but also change the physical and chemical properties of the surface and interface after coating, which can effectively alleviate side reactions and improve the stability of active materials under high voltage. Reduce battery thermal effect.
  • Surface coating can effectively broaden the working voltage window of active materials, greatly improving and optimizing the energy density of materials.
  • the surface coating modification of layered materials mainly focuses on oxides with large band gaps, such as Al 2 O 3 , ZrO 2 , TiO 2 and ZnO, or some solid electrolytes such as Li 3 PO 3 , LiPON, Li 4 Ti 5 O 12 etc.
  • oxides with large band gaps such as Al 2 O 3 , ZrO 2 , TiO 2 and ZnO, or some solid electrolytes such as Li 3 PO 3 , LiPON, Li 4 Ti 5 O 12 etc.
  • These surface coatings generally have certain ionic conductivity and high electrochemical stability, but low electronic conductivity, which is unfavorable for enhancing the interfacial dynamics of layered material electrodes.
  • the purpose of this application is to provide an improved lithium-ion battery positive electrode material and its preparation method and application.
  • One aspect of the present application discloses a lithium-ion battery positive electrode material.
  • the surface interface of the crystal structure of the lithium-ion battery positive electrode material has a layer of conductivity and lithium conduction, and does not participate in the electrochemical side reaction or chemical side effect of the interface between the electrode and the solution. Reactive high electron conductivity inorganic compound layer.
  • the side reactions in this application refer to other reactions except lithium ion deintercalation reactions.
  • this application focuses on innovation and improvement on how to improve the conductivity of the interface layer oxide.
  • This application mainly introduces a large number of oxygen vacancies at the surface interface of the crystal structure through element replacement/doping to form the inorganic compound layer of the application, for example, through doping and/or element replacement in aluminum oxide, zinc oxide, titanium oxide, indium oxide
  • a large number of oxygen vacancies are artificially created in the crystal structure of tin oxide, tin oxide and zirconium oxide, which significantly improves the electronic conductivity of the inorganic compound layer at the interface, which has a significant effect on reducing the polarization of the electrode/solution interface in the electrochemical process.
  • the lithium ion battery positive electrode material of the present application has high capacity, rate and cycle stability under high voltage. It can be understood that this application is to optimize and improve the surface interface of the crystal structure of the positive electrode material of lithium-ion batteries, thereby improving the electronic conductivity and realizing the optimization of electrode performance, not a simple surface coating modification.
  • the inorganic compound layer is epitaxially grown from the same crystal lattice of the bulk layered material.
  • the thickness of the inorganic compound layer is less than or equal to 5 nm.
  • the inorganic compound layer contains 0.1%-5.0% of oxygen defects, specifically including at least one of the following oxides;
  • Lithium oxyfluoride containing part of F substituted for O (1) Lithium oxyfluoride containing part of F substituted for O;
  • the elemental composition of the lithium oxyfluoride containing part of F substituted for O further includes Al and/or Co.
  • the Zn-doped alumina is Al 2 O 3 ⁇ xZnO, where 0.01 ⁇ x ⁇ 0.10.
  • the Nb-doped titanium oxide is Nb x Ti 1-x O
  • the In-doped titanium oxide is In y Ti 1-y O, wherein, 0.01 ⁇ x ⁇ 0.10, 0.01 ⁇ y ⁇ 0.10.
  • the Ca doped zirconia is ZrO 2 ⁇ xCaO
  • the Mg doped zirconia is ZrO 2 ⁇ yMgO
  • the B doped zirconia is ZrO 2 ⁇ zB 2 O 3
  • the Y doped zirconia is ZrO 2 ⁇ zB 2 O 3 .
  • the mixed zirconia is ZrO 2 ⁇ rY 2 O 3 , wherein, 0.01 ⁇ x ⁇ 0.10, 0.01 ⁇ y ⁇ 0.10, 0.005 ⁇ z ⁇ 0.05, 0.005 ⁇ r ⁇ 0.05.
  • Al-doped ZnO is ZnO ⁇ xAl 2 O 3
  • B-doped ZnO is ZnO ⁇ yB 2 O 3
  • In-doped ZnO is ZnO ⁇ yIn 2 O 3 , where 0.005 ⁇ x ⁇ 0.05, 0.005 ⁇ y ⁇ 0.05, 0.005 ⁇ z ⁇ 0.05.
  • the Zn-doped SnO 2 is SnO 2 ⁇ xZnO
  • the Al-doped SnO 2 is SnO 2 ⁇ yAl 2 O 3 , wherein 0.01 ⁇ x ⁇ 0.10, 0.005 ⁇ y ⁇ 0.05.
  • Zn-doped In 2 O 3 is In 2 O 3 ⁇ xZnO
  • Sn-doped In 2 O 3 is In 2 O 3 ⁇ ySnO 2 , wherein, 0.01 ⁇ x ⁇ 0.10, 0.01 ⁇ y ⁇ 0.10.
  • the specific selection of the inorganic compound at the surface and interface of the positive electrode material in the present application is mainly based on how to improve the electronic conductance of the inorganic compound at the interface layer.
  • a comparatively high-density compound was produced in the crystal structure of aluminum oxide, zinc oxide, titanium oxide, indium oxide, tin oxide, and zirconium oxide by means of element doping/replacement. many oxygen vacancies.
  • the purpose of adjusting the elemental composition of the interface inorganic compound layer used in this application is to better serve the goal of improving the electron conductance of the interface inorganic compound.
  • the above specific selection is only the inorganic compound layer specifically formed in one implementation mode of the present application.
  • element doping/replacement optimized aluminum oxide, zinc oxide, titanium oxide, indium oxide, tin oxide and zirconium oxide it is not excluded that there may also be Inorganic compound layer composed of other components.
  • the positive electrode material of the lithium ion battery is a layered positive electrode material of the general formula Li 1+x TMO 2+y , wherein, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, TM is a transition metal, TM is selected from at least one of Co, Ni, Mn and Al.
  • the positive electrode material of the lithium ion battery is at least one of lithium cobalt oxide, high-nickel binary material, high-nickel multi-component material, and lithium-rich manganese positive electrode material; wherein, high nickel means that the nickel content is greater than Or equal to 50%.
  • binary materials and multiple materials refer to positive electrode materials containing two or more of nickel, cobalt, manganese, aluminum, etc.; that is, binary materials are positive electrode materials containing two of them; Two or more positive electrode materials.
  • the positive electrode material of the lithium ion battery is at least one of LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.5 Co 0.3 Mn 0.2 O 2 and LiCoO 2 .
  • the transition metal is selected from at least one of Co, Ni, Mn and Al, which are relatively common layered positive electrode materials for lithium-ion batteries, and other transition metals are not excluded. It can be understood that the above specific battery layered positive electrode materials are only several kinds of lithium ion battery layered positive electrode materials specifically prepared in an implementation mode of the present application, and other battery layered positive electrode materials are not excluded.
  • the other side of the present application discloses the preparation method of the positive electrode material of the lithium ion battery of the present application, including carrying out the following treatment on the positive electrode material of the conventional lithium ion battery to obtain the positive electrode material of the lithium ion battery with an inorganic compound layer on the surface interface of the crystal structure:
  • Step 1 using at least one of the following methods to pretreat conventional lithium-ion battery cathode materials,
  • Liquid - phase solution pretreatment including soaking conventional lithium -ion battery cathode materials in In a solution of at least one of + , ZrO 3 2- , F - , Y 3+ and borate, the liquid phase treatment condition is 25-90°C for 1-36 hours to obtain a pretreated battery layered positive electrode material;
  • Step 2 Sinter the pretreated battery layered cathode material obtained in Step 1 at 300-700°C for 1-24 hours in an inert atmosphere or a reducing atmosphere, and cool down naturally to obtain a crystal structure with an inorganic compound layer on the surface interface Lithium-ion battery cathode material.
  • conventional lithium-ion battery positive electrode materials refer to lithium-ion battery positive electrode materials whose surface is a Li-O interface with a normal crystal structure or the interface is partially doped with TM-O.
  • the present application directly performs pretreatment and subsequent heat treatment on the conventional lithium-ion battery positive electrode material to obtain the lithium-ion battery positive electrode material with a crystal structure and an inorganic compound layer with high electronic conductivity on the surface interface of the present application.
  • the inorganic compound with high electronic conductivity on the surface of the layered material after step 1 and step 2 is chemically bonded to the bulk layered material, and the structure shows the same lattice epitaxial growth characteristics, and the surface area
  • the thickness of the inorganic compound with high electronic conductivity is less than or equal to 5nm.
  • the inert atmosphere used in the preparation method of the present application is N2 and/or Ar; the reducing atmosphere is an atmosphere of N2 plus H2 , or an atmosphere of Ar plus H2 .
  • the chemical bonding of the inorganic compound with high electronic conductivity on the surface of the layered positive electrode material and the bulk layered material and the two characteristics of homogeneous epitaxial growth are realized through the heat treatment process in step 2 . It is understandable that without the features of chemical bonding and iso-lattice epitaxial growth, the structural integrity of layered cathode materials and the Li-ion intercalation/extraction kinetics during charge and discharge cannot be guaranteed. At the same time, it should be noted that this application optimizes and regulates the heat treatment temperature/time and heat treatment atmosphere conditions in step 2, while achieving chemical bonding and homogeneous epitaxial growth, reducing the surface inorganic compound layer and layered structure as much as possible.
  • the interdiffusion between positive electrode materials keeps the oxygen vacancies in the surface inorganic compound, thereby obtaining an interfacial inorganic compound layer with high electronic conductivity. It can be understood that if the heat treatment temperature is too high or the heat treatment time is too long in step 2, or the material is treated in an oxidative atmosphere containing oxygen, the oxygen vacancies in the surface inorganic compound layer will disappear, and high electronic conductivity cannot be obtained.
  • the thickness of the inorganic compound with high electronic conductivity in the surface area must be less than or equal to 5 nm.
  • the conductive inorganic compound layer with a thickness less than or equal to 5nm is mainly to reduce the diffusion distance of the intercalation/extraction interface inorganic compound layer of lithium ions, reduce the diffusion energy barrier, and improve the diffusion kinetics. It can be understood that when the thickness of the inorganic compound layer is higher than 5 nm, although the electronic conductivity of the compound layer at the interface is high, the diffusion of lithium ions at the interface is hindered, which is also not conducive to the performance of capacity and rate performance.
  • Another aspect of the present application discloses the application of the lithium-ion battery cathode material of the present application in the preparation of power batteries, large-scale energy storage batteries, or ion batteries for 3C consumer electronics products, drones or electronic cigarettes.
  • the lithium-ion battery positive electrode material of the present application has the advantages of high capacity at high voltage, high rate and good cycle stability, and can be better used for power batteries and large-scale energy storage batteries, such as electric vehicles or other Power supply for medium and large electric equipment or energy storage power station.
  • the lithium-ion battery cathode material of the present application can also be used in lithium-ion batteries of 3C consumer electronics products, unmanned aerial vehicles or electronic cigarettes.
  • Another aspect of the present application discloses a lithium ion battery using the lithium ion battery cathode material of the present application.
  • the lithium ion battery of the present application due to the use of the lithium ion battery cathode material of the present application, enables the battery to work at a higher charge and discharge voltage, and has a higher reversible charge and discharge capacity and rate, and cycle stability better.
  • the anode material of the lithium ion battery of the present application can block the transition metal and the electrolyte, suppress the catalytic decomposition of the transition metal ion to the electrolyte under high voltage, reduce the side reaction of the electrode surface in the cycle process, and by reducing the Li increases the intercalation kinetics, so that the lithium-ion battery cathode material of the present application also has the advantages of high capacity, high rate and good cycle stability under high voltage.
  • the preparation method of the positive electrode material for lithium ion batteries of the present application is simple and easy for large-scale industrial production.
  • Fig. 1 is the XRD refinement result of the LiCoO 2 @O d -Al 2 O 3-x material in the example of the present application;
  • Fig. 2 is the TEM-mapping result of the LiCoO 2 @O d -Al 2 O 3-x material in the example of the present application;
  • Figure 3 is the electrochemical rate performance results of LiCoO 2 @O d -Al 2 O 3-x materials and commercial LiCoO 2 in the examples of this application; among them, (a) is LiCoO 2 @O d -Al 2 O 3 The electrochemical rate performance results of -x materials, (b) shows the electrochemical rate performance results of commercial LiCoO 2 ;
  • Figure 4 is the cycle stability test results of LiCoO 2 @O d -Al 2 O 3-x material and commercial LiCoO 2 in the examples of the present application;
  • Fig. 5 is the XRD refinement result of LiCoO 2 @Li-Al-Co-OF material in the example of the present application;
  • Figure 6 shows the rate performance of the LiCoO 2 @Li-Al-Co-OF material in the embodiment of the present application at 0.2-8C in the 3-4.6V vs. Li/Li + potential range;
  • Fig. 7 shows the 1C cycle performance of the LiCoO 2 @Li-Al-Co-OF material in the example of the present application in the potential range of 3-4.6V vs. Li/Li + .
  • inorganic layered cathode materials including LiCoO 2 , NMC and NCA materials
  • problems under high voltage including electrolyte decomposition leading to increased internal resistance, electrode material lattice collapse and oxygen loss, etc.
  • These problems restrict the further improvement of the electrochemical performance of layered cathode materials.
  • Optimizing the interface of the positive electrode material by coating, suppressing the degradation of the crystal structure of the material under high voltage and delaying the side reaction at the interface is a relatively common strategy at present.
  • the focus of research on the physical and chemical properties of the coating layer was to improve ionic conductance and not participate in redox reactions, but there were few studies on optimizing the interface from the perspective of improving electronic conductance.
  • the research of this application shows that by improving the electronic conductance of the surface interface of the crystal structure of the layered positive electrode material, the interface polarization can be effectively reduced, thereby obtaining a lower internal resistance of the battery, and effectively helping to increase the power of the battery.
  • the catalytic effect of the transition metal layer of the layered cathode material on the electrolyte at high voltage is the key to the thermal effect and the increase in internal resistance.
  • the research of this application found that by physically isolating the direct contact between the electrolyte and the electrode material, the catalytic effect can be effectively suppressed, the occurrence of side reactions can be greatly suppressed, the interface optimization of the positive electrode material can be maintained, and high cycle stability can be obtained.
  • the present application starts from improving the electronic conductance of the interface inorganic compound layer, forming a layer of interface inorganic compound layer that is conductive, lithium-conducting, and does not participate in electrochemical reactions, and inhibits the interfacial catalysis of the transition metal layer under high voltage. While improving the interfacial stability, the intercalation kinetics of Li + at the interface is improved, resulting in high capacity and rate performance.
  • the present application provides a lithium-ion battery positive electrode material, the surface interface of the crystal structure of the lithium-ion battery positive electrode material has a layer of conduction and lithium conduction, and does not participate in the electrochemical side reaction or chemical side reaction of the interface between the electrode and the solution.
  • layer of inorganic compounds is formed by replacing/doping elements on the surface interface of the crystal structure; for example, using B, Al, Mg, Ca, Zn, Zr, Ti, In, Sn and At least one of Y replaces part of the lithium and/or transition metal at the surface interface, and/or replaces part or all of the oxygen at the surface interface with fluorine.
  • This application replaces the inorganic compound layer formed by surface interface elements, introduces conductivity to reduce polarization resistance, and at the same time improves high voltage stability by physically isolating the direct contact between the transition metal layer of the layered material and the electrolyte; therefore, it has many advantages. It not only conducts electricity, guides lithium, does not participate in electrochemical reactions, but also suppresses side reactions, and exhibits high capacity, rate and cycle stability at high voltages.
  • the inorganic compound layer replaced by surface interface elements is mainly formed by performing pretreatment and heat treatment on conventional lithium-ion battery cathode materials.
  • the pretreatment is similar to the surface coating modification of the prior art; the difference is that the subsequent heat treatment after the pretreatment according to the conditions of the present application can more effectively realize the element replacement of the crystal structure surface interface of the layered positive electrode material . Therefore, the composite layered electrode material for a high-voltage lithium ion battery of the present application has a simple preparation method and is easy to realize industrialization.
  • lithium cobalt oxide and lithium cobalt oxide were firstly prepared as raw materials, and then lithium cobalt oxide was pretreated and heat-treated to obtain lithium cobalt oxide in which the surface interface of the crystal structure of this example was replaced by elements to form an inorganic compound layer.
  • the specific preparation method is as follows:
  • Lithium cobaltate material sintering preparation Lithium carbonate and cobalt tetroxide (D 50 between 4-8 microns) are evenly mixed according to the Li/Co ratio of 1.03, and the evenly mixed mixed powder is sieved by a 100-mesh sieving machine, and set aside. The mixed samples that were mixed evenly and sieved were sintered at 1000°C for 12h in an air atmosphere. The obtained LCO material was crushed and sieved through a 100-mesh sieving machine, and then sintered again in an air atmosphere at 900° C. for 6 h. The obtained powder sample was crushed again and sieved through a 100-mesh sieve powder machine to obtain qualified lithium cobaltate (LiCoO 2 ) powder for future use.
  • Lithium carbonate and cobalt tetroxide D 50 between 4-8 microns
  • Step 2 subsequent heat treatment, heat-treat the above-mentioned pretreated LiCoO 2 powder in an air atmosphere at 600°C for 6 hours, then lower the temperature naturally, and pass the obtained powder through a 100-mesh sieve to obtain an inorganic compound layer with ⁇ -Al 2 O 3- structure lithium cobaltate of high-mobility monovalent cation oxides, that is, alumina with vacancies in the inorganic compound layer, marked as LiCoO 2 @O d -Al 2 O 3-x .
  • x 0.01-0.50.
  • Electrochemical test Using NMP as a solvent, LiCoO 2 @O d -Al 2 O 3-x , carbon black and PVDF were uniformly mixed in a mass ratio of 8:1:1 to prepare a positive electrode sheet.
  • the active material loading About 4.5mg cm -2 .
  • the physical properties and electrochemical properties of the prepared LiCoO 2 @O d -Al 2 O 3-x material were characterized by XRD refinement, and the results are shown in Figure 1.
  • the results in Fig. 1 show that the obtained LiCoO 2 @O d -Al 2 O 3-x is completely consistent with the layered structure of standard conventional lithium cobalt oxide.
  • the TEM EDS-mapping results are shown in Figure 2.
  • the results in Figure 2 show that Al elements are enriched at the surface interface of LiCoO 2 @O d -Al 2 O 3-x .
  • the test results of the rate performance of the battery are shown in Figure 3.
  • the results in Figure 3 show that the LiCoO 2 @O d -Al 2 O 3-x material has a discharge capacity of 231mAh g -1 at a current density of 0.2C, and a median voltage of 4.035V, the energy density of the positive electrode active material is 932Wh/kg; LiCoO 2 @O d -Al 2 O 3-x material has a discharge capacity of 179mAh g -1 at a current density of 8C, and the median voltage is 3.948V, the positive electrode active material The energy density exceeds 708Wh/kg.
  • the test results of the battery 1C after 200 cycles are shown in Figure 4.
  • the results in Figure 4 show that after 100 cycles, the capacity retention rate is 81%.
  • Example 2 the same lithium cobaltate powder as in Example 1 was used for pretreatment and heat treatment, and the surface interface of the crystal structure of this example was replaced with lithium cobaltate to form an inorganic compound layer.
  • the difference is that the specific materials and conditions of the pretreatment and heat treatment in this example are different. details as follows:
  • Step 1 pretreatment, add 4g of LiCoO 2 prepared in Example 1 to 80mL of deionized water, and keep stirring evenly to obtain suspension A; add 0.15g of aluminum sulfate to 40mL of deionized water, stir and dissolve to obtain solution B ; Add 0.10 g of ammonium fluoride to 40 mL of deionized water, stir and dissolve to obtain solution C.
  • solution B was added dropwise to suspension A to form solution D; after solution D was stirred for 10 minutes, solution C was added dropwise to solution D to form suspension Turbid liquid E.
  • filter the suspension with deionized water and alcohol dry in a vacuum oven at 80°C, and pass through a 100-mesh sieve for later use;
  • Step 2 heat treatment and sintering, the above-mentioned pretreated LiCoO 2 powder is heat-treated at 500°C for 6 hours in an air atmosphere, and then the temperature is naturally lowered, and the obtained powder is sieved with 100 meshes to obtain an inorganic compound layer with oxygen defects.
  • Lithium cobaltate of lithium oxyfluoride labeled as LiCoO2 @Li-Al-Co-OF.
  • Electrochemical test Using NMP as a solvent, LiCoO 2 @Li-Al-Co-OF, carbon black and PVDF were uniformly mixed at a mass ratio of 8:1:1 to prepare a positive electrode sheet with an active material loading of about 4.5 mg cm -2 .
  • the physical properties and electrochemical properties of the prepared LiCoO 2 @Li-Al-Co-OF material were characterized by XRD refinement, and the results are shown in Figure 5.
  • the results in Fig. 5 show that the obtained LiCoO 2 @Li-Al-Co-OF is completely consistent with the standard conventional lithium cobalt oxide layered lithium cobalt oxide.
  • the test results of the battery rate performance are shown in Figure 6.
  • the results in Figure 6 show that the LiCoO 2 @Li-Al-Co-OF material has a discharge capacity of 228mAh g -1 and a median voltage of 4.042V at a current density of 0.2C.
  • the energy density of the positive electrode active material is 924Wh/kg; LiCoO 2 @Li-Al-Co-OF material has a discharge capacity of 193mAh g -1 and a median voltage of 3.956V at a current density of 8C, and the energy density of the positive electrode active material exceeds 764Wh/kg.
  • the test results of the battery 1C after 200 cycles are shown in Figure 7. The results in Figure 7 show that after 200 cycles, the capacity retention rate exceeds 85%. Therefore, the LiCoO 2 @Li-Al-Co-OF material prepared in this example exhibits excellent rate and cycle stability at high voltage.
  • Example 2 the same lithium cobaltate powder as in Example 1 was used for pretreatment and heat treatment, and the surface interface of the crystal structure of this example was replaced with lithium cobaltate to form an inorganic compound layer.
  • the difference is that the specific materials and conditions of the pretreatment and heat treatment in this example are different. details as follows:
  • Step 1 synthesis of nano-excipients and pretreatment, weigh CaO and ZrOCl 2 8H 2 O according to the molar ratio of 0.05:1, and dissolve them with a 5:1 dilute nitric acid solution to form solution A; slowly drop solution A into the solution In an ammonia solution containing polyethylene glycol, react under magnetic stirring conditions for 2 hours, age, filter with suction, wash with deionized water and absolute ethanol, and dry in vacuum at 80°C for 24 hours to obtain a nano-powder for use; mix the above powder with Lithium cobaltate powder is mixed evenly at a mass ratio of 0.025:0.975, and ground for 30 minutes until completely uniform by ball milling, and the obtained mixed powder is sieved through a 100-mesh sieve, and set aside;
  • Step 2 heat treatment and sintering, the above pretreated mixed powder is heat-treated at 500°C for 6 hours in an air atmosphere, and then the temperature is naturally lowered, and the obtained powder is sieved with 100 mesh to obtain cobalt coated with ZrO 2 ⁇ 0.05CaO on the surface Lithium oxide powder, marked as LiCoO 2 @ZrO 2 ⁇ 0.05CaO.
  • Electrochemical test Using NMP as a solvent, LiCoO 2 @ZrO 2 ⁇ 0.05CaO, carbon black and PVDF were uniformly mixed at a mass ratio of 8:1:1 to prepare a positive electrode sheet with an active material loading of about 4.5mg cm -2 .
  • the refined XRD results of the prepared LiCoO 2 @ZrO 2 ⁇ 0.05CaO material in this example show that the obtained LiCoO 2 @ZrO 2 ⁇ 0.05CaO is completely consistent with the standard conventional lithium cobalt oxide layered lithium cobalt oxide.
  • the test results of battery rate performance show that LiCoO 2 @ZrO 2 ⁇ 0.05CaO material has a discharge capacity of 236mAh g -1 at a current density of 0.2C, a median voltage of 4.042V, and an energy density of 954Wh/kg as a positive electrode active material; LiCoO 2 @ZrO 2 ⁇ 0.05CaO material has a discharge capacity of 203mAh g -1 and a median voltage of 3.965V at a current density of 8C, and the energy density of the positive active material exceeds 805Wh/kg.
  • the test results of the battery 1C after 200 cycles show that the capacity retention rate exceeds 86% after 200 cycles. Therefore, the LiCoO 2 @ZrO 2 ⁇ 0.05CaO material prepared in this example exhibits excellent rate and cycle stability at high voltage.
  • LiCoO 2 @ZrO 2 ⁇ 0.025Y 2 O 3 was also prepared by the same method in this example. It was found through electrochemical tests that the discharge capacity was 232mAh g -1 and the median voltage was 4.036V, the energy density of the positive electrode active material is 936Wh/kg; at a current density of 8C, the discharge capacity is 196mAh g -1 , the median voltage is 3.969V, and the energy density of the positive electrode active material exceeds 778Wh/kg. Therefore, the LiCoO 2 @ZrO 2 ⁇ 0.05CaO material prepared in this example also exhibits excellent rate and cycle stability under high voltage.
  • the powder of the layered positive electrode material is pretreated and heat-treated by the same method as in Example 3 to obtain the layered positive electrode material in which the surface interface of the crystal structure of this example forms an inorganic compound layer through element replacement.
  • the specific materials for the pretreatment and heat treatment in this example are LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) and LiNi 0.5 Co 0.3 Mn 0.2 O 2 (NCM532).
  • the materials after steps 1 to 3 were named NCM811@ZrO 2 ⁇ 0.05CaO and NCM532@ZrO 2 ⁇ 0.05CaO respectively.
  • NCM811@ZrO 2 ⁇ 0.05CaO was electrochemically tested by the same method as in Example 3, and it was found that the discharge capacity was 216mAh g -1 at a current density of 0.2C and in the range of 3-4.3V; at a current density of 8C , the discharge capacity was 126mAh g -1 .
  • NCM811@ZrO 2 prepared by the same method has a discharge capacity of 188mAh g -1 and 92mAh g -1 at 0.2C and 8C, respectively.
  • NCM532@ZrO 2 ⁇ 0.05CaO was electrochemically tested by the same method as in Example 3, and it was found that the discharge capacity was 236mAh g -1 at a current density of 0.2C and in the range of 3-4.3V; at a current density of 8C , the discharge capacity was 116mAh g -1 .
  • NCM532@ZrO 2 prepared by the same method has a discharge capacity of 157mAh g -1 and 63mAh g -1 at 0.2C and 8C, respectively.
  • NCM811@ZrO 2 ⁇ 0.05CaO and NCM532@ZrO 2 ⁇ 0.05CaO obtained by element doping/replacement have higher capacity and rate performance than NCM811@ZrO 2 and NCM532@ZrO 2 .
  • the lithium cobaltate powder is pretreated and heat-treated by the same method as in Example 3, and the surface interface of the crystal structure of this example is replaced by elements to form the lithium cobaltate layer of the inorganic compound.
  • the CaO and ZrOCl 2 ⁇ 8H 2 O added in step 1 are replaced to obtain inorganic compound layers with different compositions in the surface region of lithium cobaltate.
  • the oxides behind the "@" symbol in Table 1 are inorganic compound layers.
  • the results in Table 1 show that compared with pure aluminum oxide, zinc oxide, titanium oxide, tin oxide, and indium oxide as the lithium cobaltate cathode material of the interface inorganic compound layer, after element doping of the corresponding oxide, due to the existence of oxygen vacancies As a result, the electronic conductance of the surface inorganic compound layer increases, and the capacity and rate performance of the cathode material are significantly improved.

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Abstract

La présente demande concerne un matériau d'électrode positive pour une batterie lithium-ion, son procédé de préparation et son application. Selon le matériau d'électrode positive pour une batterie lithium-ion de la présente demande, une interface de surface d'une structure cristalline correspondante est pourvue d'une couche de composé inorganique à conductivité d'électrons élevée qui est électroconductrice et conductrice de lithium et ne participe pas à une réaction secondaire électrochimique ni à une réaction secondaire chimique sur une interface entre une électrode et une solution. Selon le matériau d'électrode positive pour une batterie lithium-ion de la présente demande, la couche de composé inorganique correspondante peut bloquer un métal de transition d'un électrolyte, ce qui permet d'inhiber l'effet de décomposition catalytique des ions de métal de transition sur l'électrolyte sous haute tension et de réduire la réaction secondaire sur la surface de l'électrode dans un procédé cyclique ; de plus, la cinétique d'incorporation de Li+ est accrue par réduction de la polarisation de l'électrode, de telle sorte que le matériau d'électrode positive pour une batterie lithium-ion de la présente demande présente également les avantages d'être de capacité élevée, de vitesse élevée, de stabilité cyclique satisfaisante et similaire sous haute tension. De plus, le procédé de préparation du matériau d'électrode positive pour une batterie lithium-ion de la présente demande est simple, et est facile à réaliser à une échelle industrielle de grande ampleur.
PCT/CN2021/122866 2021-10-09 2021-10-09 Matériau d'électrode positive pour batterie lithium-ion, son procédé de préparation et son application Ceased WO2023056635A1 (fr)

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