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WO2018145565A1 - Matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et son procédé de préparation - Google Patents

Matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et son procédé de préparation Download PDF

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WO2018145565A1
WO2018145565A1 PCT/CN2018/073234 CN2018073234W WO2018145565A1 WO 2018145565 A1 WO2018145565 A1 WO 2018145565A1 CN 2018073234 W CN2018073234 W CN 2018073234W WO 2018145565 A1 WO2018145565 A1 WO 2018145565A1
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Prior art keywords
positive electrode
lithium ion
solid
solid electrolyte
ion battery
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Chinese (zh)
Inventor
马丽
张琦
袁圣杰
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NIO Co Ltd
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NIO Co Ltd
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Priority claimed from CN201710072193.5A external-priority patent/CN107017388A/zh
Priority claimed from CN201710070715.8A external-priority patent/CN107017387A/zh
Application filed by NIO Co Ltd filed Critical NIO Co Ltd
Publication of WO2018145565A1 publication Critical patent/WO2018145565A1/fr
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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
    • 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 invention belongs to the technical field of batteries.
  • the present invention relates to a positive electrode material for a lithium ion battery and a method of preparing the same, and more particularly to a composite positive electrode material for a solid state lithium ion battery and a method of preparing the same.
  • Lithium-ion battery is a new type of rechargeable battery with high voltage, high energy density, environmental protection and pollution-free. It is known as "the most promising chemical power source”. With the rise of the low-carbon economy, lithium-ion batteries are actively developing in the direction of automobile power and grid energy storage.
  • the traditional structure of the power-type lithium-ion battery has the characteristics of high voltage, high energy density, good cycle performance, etc., and is widely used in portable digital products such as mobile phones, cameras, and notebook computers, and is gradually being applied in the field of electric bicycles, but
  • a flammable and explosive organic carbonate-based electrolyte as an organic electrolyte solution causes electrolyte leakage and the resulting battery explosion, fire, and the like to occur frequently.
  • An effective way to improve the safety of lithium-ion batteries is to use solid electrolytes, which greatly improve safety while simplifying battery safety devices while reducing costs.
  • the interface state between the solid electrolyte and the electrode active material directly affects battery performance. Mainly because the contact between the solid electrolyte and the electrode is not good, the contact resistance between the two is increased, and the internal resistance of the whole battery is too large, and lithium ions cannot move smoothly between the electrode and the electrolyte, thereby reducing The battery capacity also results in lower durability and higher interface resistance.
  • One of the prior art methods for preparing a solid-state lithium ion battery is to mix and coat a solid electrolyte precursor and a positive electrode active material in a certain ratio, and then to obtain an electrode by high-temperature sintering.
  • the use of a conventional liquid lithium ion battery electrode production line to prepare solid state lithium ion battery electrodes requires the addition of high temperature sintering equipment on this line (see Figure 1).
  • Another prior art method for preparing a solid-state lithium ion battery is to apply a positive electrode active material and a solid electrolyte layer in a certain ratio according to a certain ratio, press, cut, laminate, etc., and then perform high-temperature sintering after lamination to obtain a desired Solid state lithium ion battery electrode (see Figure 1).
  • This method also needs to increase the high-temperature sintering equipment in the traditional liquid lithium ion electrode production line, and needs to modify the liquid lithium ion battery production line, the cost is high, and the continuity of the original liquid lithium ion battery electrode production line is destroyed.
  • One technical problem to be solved by the present invention is that the existing ceramic-based solid electrolyte can only function as lithium ion conduction, and cannot store lithium ions as an active material, resulting in a decrease in energy density of the battery.
  • One technical problem to be solved by the present invention is to avoid damage to the continuity of the existing liquid lithium ion battery electrode production line during the preparation of the solid lithium ion battery electrode.
  • a composite positive electrode material for a solid-state lithium ion battery comprising a positive electrode active material, a solid electrolyte, and an organic compound additive, wherein the weight of the positive electrode active material, the solid electrolyte, and the organic compound additive is provided
  • the ratio is 80 to 88:5 to 15:2 to 8.
  • a method of preparing a composite positive electrode material for a solid state lithium ion battery comprising the steps of:
  • the mixture powder is sintered at a high temperature to obtain the composite positive electrode material containing a solid electrolyte and a positive electrode active material in the form of a powder.
  • a method of producing a composite positive electrode material of the first aspect of the invention comprising:
  • a method for preparing a positive electrode of a solid state lithium ion battery comprising the steps of:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is applied onto a positive electrode substrate, dried, compacted, and slit to obtain a positive electrode.
  • a solid state lithium ion battery positive electrode obtained by the above-described method for producing a solid state lithium ion battery positive electrode.
  • a method of fabricating a solid state lithium ion battery comprising the steps of:
  • the positive electrode and the negative electrode are laminated and assembled with a solid electrolyte to obtain a solid state lithium ion battery.
  • a solid state lithium ion battery obtained by the above-described method for producing a solid state lithium ion battery.
  • the invention provides a method for pre-mixing a solid electrolyte and a positive electrode active material and then coating the existing problems in the production method of the existing solid-state lithium ion battery.
  • the interfacial resistance between the solid electrolyte and the positive electrode material can be reduced by the preparation method of the composite positive electrode material of the present invention.
  • the composite positive electrode material obtained by the preparation method of the composite positive electrode material of the present invention can be used for preparing a solid lithium ion battery without changing the conventional liquid lithium ion battery electrode production line.
  • the preparation method of the positive electrode of the solid state lithium ion battery of the invention can be carried out without changing the electrode production line of the conventional liquid lithium ion battery, and the equipment transformation cost for preparing the solid lithium ion battery by modifying the liquid lithium ion battery production line can be greatly reduced.
  • the lithium ion of the solid electrolyte of the solid-state lithium ion battery of the present invention has high conductivity, low internal resistance, and good rate discharge performance.
  • the invention also improves the energy density of the solid state lithium ion battery by mixing the active material or the precursor material of the electrode with the organic compound having the lithium ion storage ability and a small amount of the solid electrolyte to prepare the electrode.
  • the preparation method of the composite positive electrode material of the present invention is not limited to the preparation of the positive electrode material of the solid lithium ion battery, and can also be used for the preparation of the positive electrode material of the sodium ion battery, as long as the corresponding solid electrolyte or its precursor and the positive electrode active material or The precursor can be replaced. Also, the preparation method of the positive electrode of the solid state lithium ion battery of the present invention and the preparation method of the solid state lithium ion battery are also the same.
  • FIG. 1 schematically shows a method of preparing a conventional solid state lithium ion battery, wherein sintering is optionally performed before or prior to rolling.
  • Fig. 2 schematically shows a method of preparing a solid state lithium ion battery of the present invention, in which a conventional liquid lithium ion battery production line is shown in a dotted line.
  • a composite positive electrode material for a solid-state lithium ion battery comprising a positive electrode active material, a solid electrolyte, and an organic compound additive, wherein the weight of the positive electrode active material, the solid electrolyte, and the organic compound additive is provided
  • the ratio is 80 to 88:5 to 15:2 to 8.
  • the positive active material may be a solid cathode active material commonly used in solid lithium ion batteries in the field, such as lithium cobaltate, lithium manganate, nickel manganese material, lithium iron phosphate, nickel cobalt manganese, nickel cobalt aluminum ternary material, and Sulfur-containing materials.
  • the nickel manganese material may be LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Mn 0.5 O 2 or the like.
  • the sulfur-containing material may be S, Li 2 S, or the like.
  • NASICON type lithium ion conductor Li 1+x Ti 2-x M x (PO 4 )
  • the organic compound additive may be selected, for example, from a metal organic framework material (MOF), an oxygen-containing conjugated organic substance, a conductive high molecular weight, an organic sulfide, and the like.
  • MOF metal organic framework material
  • oxygen-containing conjugated organic compound examples include 1,4,5,8-tetrahydroxy-9,10-fluorene (THAQ), tetrahydrohexafluorene (THHQ), and benzohexacene (DBHQ). ), 2,4,7-trinitro-9-fluorenone (TNF), and the like.
  • THAQ 1,4,5,8-tetrahydroxy-9,10-fluorene
  • THHQ tetrahydrohexafluorene
  • DBHQ benzohexacene
  • TNF 2,4,7-trinitro-9-fluorenone
  • polyacetylene polyparaphenylene, polyaniline, polypyrrole, polythiophene and the like can be mentioned.
  • organic sulfide examples include poly 2,5-dimercapto-thiadiazole, poly 2,2-dithiodiphenyl (PDTDA), 14-phenylene-1, 2, 4 - Dithiazole polymer (PPDTA) or the like.
  • the weight ratio of the positive electrode active material, the solid electrolyte, and the organic compound additive is preferably 82 to 87:8 to 12:3 to 6.
  • the weight ratio of the positive active material, the solid electrolyte, and the organic compound additive is 85:10:5.
  • a method of preparing a composite positive electrode material for a solid state lithium ion battery comprising the steps of:
  • the mixture powder is sintered at a high temperature to obtain a composite positive electrode material comprising a solid electrolyte and a positive electrode active material in the form of a powder.
  • the preparation method according to the second aspect of the invention may further comprise the following steps:
  • the solid electrolyte is contained in an amount of from 5% by weight to 40% by weight, preferably from 10% by weight to 30% by weight, more preferably from 15% by weight to 25% by weight, most preferably from 18% by weight to 22% by weight.
  • the weight is based on the total weight of the composite positive electrode material.
  • NASICON type lithium ion conductor Li 1+x Ti 2-x M x (PO 4 )
  • the precursor of the solid electrolyte based on the desired solid electrolyte.
  • the solid electrolyte is Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01
  • Li 2 CO 3 , Al(OH) 3 , GeO 2 , and NH 4 H 2 PO 4 may be selected as the solid electrolyte precursor.
  • the solid electrolyte is Li 7 La 3 Zr 2 O 12
  • lithium acetate, cerium acetate, and zirconium acetate can be selected as the solid electrolyte precursor.
  • the positive active material may be a solid cathode active material commonly used in solid lithium ion batteries in the field, such as lithium cobaltate, lithium manganate, nickel manganese material, lithium iron phosphate, nickel cobalt manganese, nickel cobalt aluminum ternary material, and Sulfur-containing materials.
  • the nickel manganese material may be LiNi 0.5 Mn 1.5 O 4 , LiNi 0.5 Mn 0.5 O 2 or the like.
  • the sulfur-containing material may be S, Li 2 S, or the like.
  • a person skilled in the art can easily determine the precursor of the positive active material from the desired positive active material.
  • the homogeneous mixing of the solid electrolyte or its precursor with the positive electrode active material or its precursor can be carried out by a mechanical mixing method commonly used in the art, such as high speed ball milling, and the obtained powder has an average particle diameter of 30 to 900 nm, preferably 50 to 500 nm. More preferably, it is 80-150 nm.
  • the sintering is carried out at 300 ° C to 1200 ° C, preferably 500 ° C to 1150 ° C, more preferably 600 ° C to 1150 ° C, most preferably 750 ° C to 1125 ° C for 8 to 24 hours, preferably 10 to 12 hours, more preferably 12 hours.
  • the sintering process can be carried out as follows: ramping to 750 ° C at 5 ° C/min and holding at 750 ° C for 12 h.
  • the sintering process can be carried out as follows: 5 ° C / min to 900 ° C, 8 ° h at 900 ° C and then warmed to 1125 ° C and then kept at 1125 ° C for 12 h.
  • the precursor powder When the precursor powder is contained in the mixture powder, the precursor reacts during the sintering to obtain a solid electrolyte or a positive electrode active material.
  • the positive active material is activated during the sintering process.
  • a method of producing a composite positive electrode material of the first aspect of the invention comprising:
  • the precursor of the solid electrolyte based on the desired solid electrolyte.
  • the solid electrolyte is Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01
  • Li 2 CO 3 , Al(OH) 3 , GeO 2 , and NH 4 H 2 PO 4 may be selected as the solid electrolyte precursor.
  • the solid electrolyte is Li 7 La 3 Zr 2 O 12
  • lithium acetate, cerium acetate, and zirconium acetate can be selected as the solid electrolyte precursor.
  • a person skilled in the art can easily determine the precursor of the positive active material from the desired positive active material.
  • the homogeneous mixing of the solid electrolyte or its precursor with the positive electrode active material or its precursor can be carried out by a mechanical mixing method commonly used in the art, such as high speed ball milling, and the obtained powder has an average particle diameter of 30 to 900 nm, preferably 50 to 500 nm. More preferably, it is 80-150 nm.
  • the sintering is carried out at 300 ° C to 1200 ° C, preferably 500 ° C to 1150 ° C, more preferably 600 ° C to 1150 ° C, for 8 to 24 hours, preferably 10 to 12 hours, more preferably 12 hours.
  • the sintering process can be carried out as follows: ramping to 600 ° C at 5 ° C/min and holding at 600 ° C for 12 h.
  • the sintering process can be carried out as follows: ramping to 1125 ° C at 5 ° C/min and holding at 1125 ° C for 12 h.
  • the precursor powder When the precursor powder is contained in the mixture powder, the precursor reacts during the sintering to obtain a solid electrolyte or a positive electrode active material.
  • the positive active material is activated during the sintering process.
  • a method for preparing a positive electrode of a solid state lithium ion battery comprising the steps of:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is applied onto a positive electrode substrate, dried, compacted, and slit to obtain a positive electrode.
  • a solid state lithium ion battery positive electrode is prepared as follows:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is applied onto a positive electrode substrate, and dried, rolled, and slit to obtain a positive electrode.
  • a solid state lithium ion battery positive electrode is prepared as follows:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is applied onto a positive electrode substrate, and dried, rolled, and slit to obtain a positive electrode.
  • the positive electrode slurry can be formulated by dissolving or dispersing a composite positive electrode material, a conductive additive, and a binder in a solvent.
  • the positive electrode slurry is formulated by mixing a composite positive electrode material, a conductive additive, and a binder, and dissolving or dispersing the resulting mixture in a solvent.
  • the conductive additive may be a conductive additive commonly used in the field of lithium ion battery preparation, such as graphite conductive agent, such as KS-6, KS-15, SFG-6, SFG-15; carbon black conductive agent, such as acetylene black, Super P Super S, 350G, carbon fiber (VGCF, carbon nanotube (CNT), Ketjen black; graphene, etc.
  • graphite conductive agent such as KS-6, KS-15, SFG-6, SFG-15
  • carbon black conductive agent such as acetylene black, Super P Super S, 350G, carbon fiber (VGCF, carbon nanotube (CNT), Ketjen black; graphene, etc.
  • the binder may be a binder commonly used in the field of lithium ion battery preparation, such as polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose. (CMC) and so on.
  • PVDF polyvinylidene fluoride
  • PVA polyvinyl alcohol
  • PTFE polytetrafluoroethylene
  • CMC sodium carboxymethyl cellulose.
  • the solvent may be a solvent commonly used in the field of lithium ion battery preparation, such as N-methylpyrrolidone (NMP) and the like.
  • NMP N-methylpyrrolidone
  • the mass ratio of the composite positive electrode material, the conductive additive, and the binder is from 80 to 90:5 to 10:5 to 10, preferably from 85 to 90:5 to 8:5 to 8.
  • the mass ratio of the composite positive electrode material, the conductive additive, and the binder is 88:6:6.
  • the mass ratio of the composite positive electrode material, the conductive additive, and the binder is 90:5:5.
  • the positive electrode substrate is a positive electrode substrate commonly used in solid state lithium ion batteries, such as aluminum foil.
  • Coating, drying, rolling, and slitting in the preparation of the positive electrode can be carried out according to process parameters known in the art.
  • the drying may be carried out by constant temperature heating drying, rotary evaporation drying or spray drying.
  • the rolling may be performed by rolling at a pressure of 5 MPa.
  • a solid state lithium ion battery positive electrode obtained by the above-described method for producing a solid state lithium ion battery positive electrode.
  • a method of fabricating a solid state lithium ion battery comprising the steps of:
  • the positive electrode and the negative electrode are laminated and assembled with a solid electrolyte to obtain a solid state lithium ion battery.
  • a solid state lithium ion battery is prepared as follows:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is coated on a positive electrode substrate, and dried, rolled, and slit to obtain a positive electrode;
  • the positive electrode and the negative electrode are laminated and assembled with a solid electrolyte to obtain a solid state lithium ion battery.
  • a solid state lithium ion battery is prepared as follows:
  • the obtained composite positive electrode material is formulated into a positive electrode slurry, and the obtained positive electrode slurry is coated on a positive electrode substrate, and dried, rolled, and slit to obtain a positive electrode;
  • the positive electrode and the negative electrode are laminated and assembled with a solid electrolyte to obtain a solid state lithium ion battery.
  • the step of obtaining the positive electrode and the step of obtaining the negative electrode are not successively required, and the positive electrode may be prepared first, or the negative electrode may be prepared first, or the positive electrode and the negative electrode may be simultaneously prepared.
  • the method of preparing the negative electrode is a method generally used in the art.
  • the negative electrode material is a negative electrode material commonly used in solid lithium ion batteries, such as graphite, lithium titanate, metallic lithium, and the like.
  • a sheet of a metal material can be directly used as a negative electrode.
  • the negative electrode material may also be formulated into a negative electrode slurry, and the obtained negative electrode slurry may be applied onto a negative electrode substrate, dried, rolled, and slit to obtain a negative electrode.
  • the negative electrode slurry is prepared by dissolving or dispersing a negative electrode material, a conductive additive, and a binder in a solvent.
  • the anode slurry is formulated as follows: a negative electrode material, a conductive additive, and a binder are mixed, and the resulting mixture is dissolved or dispersed in a solvent.
  • the conductive additive may be a conductive additive commonly used in the field of lithium ion battery preparation, such as graphite conductive agent, such as KS-6, KS-15, SFG-6, SFG-15; carbon black conductive agent, such as acetylene black, Super P , Super S, 350G, carbon fiber (VGCF), carbon nanotubes (CNT), Ketjen black; graphene and the like.
  • graphite conductive agent such as KS-6, KS-15, SFG-6, SFG-15
  • carbon black conductive agent such as acetylene black, Super P , Super S, 350G, carbon fiber (VGCF), carbon nanotubes (CNT), Ketjen black
  • graphene and the like such as graphite conductive agent, such as KS-6, KS-15, SFG-6, SFG-15
  • carbon black conductive agent such as acetylene black, Super P , Super S, 350G, carbon fiber (VGCF), carbon nanotubes (CNT), Ketjen black
  • the binder may be a binder commonly used in the field of lithium ion battery preparation, such as polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose. (CMC) and so on.
  • PVDF polyvinylidene fluoride
  • PVA polyvinyl alcohol
  • PTFE polytetrafluoroethylene
  • CMC sodium carboxymethyl cellulose.
  • the solvent may be a solvent commonly used in the field of lithium ion battery preparation, such as N-methylpyrrolidone (NMP) and the like.
  • NMP N-methylpyrrolidone
  • the mass ratio of the anode material, the conductive additive, and the binder is from 80 to 95:5 to 10:5 to 10, preferably from 85 to 90:1 to 5:5 to 10.
  • the mass ratio of the anode material, the conductive additive, and the binder is 90:1:9.
  • the negative electrode substrate is a negative electrode substrate commonly used in solid state lithium ion batteries, such as copper foil.
  • the solid electrolyte is the same as the solid electrolyte described in the first aspect of the invention.
  • the lamination, assembly, drying, rolling, slitting, and lamination, assembly of the slurry during the preparation of the negative electrode can be carried out according to process parameters known in the art.
  • the drying may be carried out by constant temperature heating drying, rotary evaporation drying or spray drying.
  • the rolling may be performed by rolling at a pressure of 5 MPa.
  • Fig. 2 schematically shows a method of preparing a solid state lithium ion battery of the present invention, which does not require a change in a liquid lithium ion battery production line.
  • the present invention avoids damage to the continuity of existing liquid lithium ion battery production lines by forming an activated positive electrode material prior to coating.
  • a solid state lithium ion battery obtained by the above-described method for producing a solid state lithium ion battery.
  • the solid lithium ion battery according to the present invention can have a higher energy density.
  • KS-6 carbon black conductive additive
  • PVDF binder, polyvinylidene fluoride
  • NMP solvent, N-methylpyrrolidone.
  • a NASICON type lithium ion conductor was selected as the solid electrolyte, LiCoO 2 was used as the positive electrode material, and the solid electrolyte precursor powder (Li 2 CO 3 :Al(OH) 3 :GeO 2 : was weighed according to the mass ratio of the solid electrolyte to the positive electrode material of 15:85, respectively.
  • NH 4 H 2 PO 4 is in accordance with Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01 stoichiometric ratio) and LiCoO 2 powder.
  • the mixed powder was ball milled using a planetary ball mill at a speed of 400 r/min and ball milled for 24 hours.
  • the powder mixture obtained by ball milling was transferred to Al 2 O 3 crucible, and the crucible was placed in a muffle furnace, and the temperature was raised to 750 ° C at 5 ° C / min, and the composite positive electrode having a particle diameter of 100 nm was obtained after being kept at 750 ° C for 12 h. Material powder.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 10 g of a mixture, and the mixture was dispersed in 5 g of NMP.
  • the mixture was uniformly stirred by a vacuum planetary mixer to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil having a thickness of 18 ⁇ m to a coating thickness of 60 ⁇ m. Further, drying was carried out in a vacuum oven at 80 ° C for 24 hours, and the dried electrode sheet was rolled (pressure controlled at 5 MPa), and the solid electrolyte composite positive electrode sheet was obtained by slitting.
  • the negative electrode slurry was obtained, and the negative electrode slurry was applied on a copper foil having a thickness of 12 ⁇ m to a coating thickness of 65 ⁇ m.
  • the mixture was further dried in a vacuum oven at 80 ° C for 24 hours, rolled (pressure controlled at 5 MPa), and slit-cut to obtain a negative electrode sheet.
  • the obtained positive and negative electrode sheets were laminated and assembled with a Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01 solid electrolyte to obtain a solid lithium ion battery.
  • the solid state lithium ion battery was discharged at 25 ° C, 0.5 C for 1 C, and the charge and discharge cycle test was carried out under the conditions of a charge and discharge cutoff voltage of 4.2 V - 2.5 V.
  • the results showed that the first discharge specific capacity was 130 mAh / g, after 100 cycles.
  • the capacity retention rate is 87%, and the degree of decline is small.
  • a NASICON type lithium ion conductor was selected as the solid electrolyte, and LiCoO 2 was used as the positive electrode material, and the solid electrolytes Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01 and LiCoO 2 powder were weighed according to the mass ratio of the solid electrolyte and the positive electrode material of 15:85, respectively.
  • the mixed powder was ball milled using a planetary ball mill at a speed of 400 r/min and ball milled for 24 hours.
  • the ball-milled mixed powder was transferred to Al 2 O 3 crucible, and the crucible was placed in a muffle furnace, and the temperature was raised to 750 ° C at 5 ° C / min, and the composite positive electrode having a particle diameter of 90 nm was obtained after being kept at 750 ° C for 12 h. Material powder.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 10 g of a mixture, and the mixture was dispersed in 5 g of NMP.
  • the mixture was uniformly stirred by a vacuum planetary mixer to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil having a thickness of 18 ⁇ m to a coating thickness of 60 ⁇ m. Further, drying was carried out in a vacuum oven at 80 ° C for 24 hours, and the dried electrode sheet was rolled (pressure controlled at 5 MPa), and the solid electrolyte composite positive electrode sheet was obtained by slitting.
  • the mixture was dispersed in 8.25 g of NMP and thoroughly stirred by a vacuum planetary mixer.
  • the negative electrode slurry was obtained, and the negative electrode slurry was coated on a copper foil having a thickness of 12 ⁇ m to a coating thickness of 65 ⁇ m.
  • the mixture was further dried in a vacuum oven at 80 ° C for 24 hours, rolled (pressure controlled at 5 MPa), and slit-cut to obtain a negative electrode sheet.
  • the obtained positive and negative electrode sheets were laminated and assembled with a Li 1.52 Al 0.5 Ge 1.5 P 3 O 12.01 solid electrolyte to obtain a solid lithium ion battery.
  • the solid-state lithium ion battery was charged and discharged at 25 ° C, 0.5 C for 1 C discharge, and the charge-discharge cut-off voltage was 4.2 V-2.5 V.
  • the results showed that the first discharge specific capacity was 128 mAh/g, after 100 cycles, The capacity retention rate is 85%, and the degree of decline is small.
  • Lithium-ion lithium ion conductor Li 7 La 3 Zr 2 O 12 was selected as the solid electrolyte
  • LiFePO 4 was used as the positive electrode material
  • the solid electrolyte Li 7 La 3 Zr 2 O 12 and the mass ratio of the solid electrolyte and the positive electrode material were respectively 20:80.
  • LiFePO 4 powder The mixed powder was ball milled using a planetary ball mill at a speed of 400 r/min and ball milled for 24 hours.
  • the ball-milled mixed powder was transferred to Al 2 O 3 crucible, and the crucible was placed in a muffle furnace, and the temperature was raised to 1125 ° C at 5 ° C / min, and the composite positive electrode having a particle diameter of 95 nm was obtained after being kept at 1125 ° C for 12 h. Material powder.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 10 g of the mixture, and the mixture was dispersed in 5 g of NMP.
  • the mixture was uniformly stirred by a vacuum planetary mixer to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil having a thickness of 18 ⁇ m to a coating thickness of 60 ⁇ m. Further, drying was carried out in a vacuum oven at 80 ° C for 24 hours, and the dried electrode sheet was rolled (pressure controlled at 5 MPa), and the solid electrolyte positive electrode sheet was obtained by slitting.
  • the negative electrode slurry was obtained, and the negative electrode slurry was applied on a copper foil having a thickness of 12 ⁇ m to a coating thickness of 65 ⁇ m.
  • the mixture was further dried in a vacuum oven at 80 ° C for 24 hours, rolled (pressure controlled at 5 MPa), and slit-cut to obtain a negative electrode sheet.
  • the obtained positive and negative electrode sheets were laminated and assembled with a Li 7 La 3 Zr 2 O 12 solid electrolyte to obtain a solid lithium ion battery.
  • the solid-state lithium ion battery was subjected to a charge-discharge cycle test at 25 ° C, 0.5 C charge 1 C discharge, charge and discharge cut-off voltage 3.7 V-2.2 V, and the results showed that the first discharge specific capacity was 120 mAh / g, after 100 cycles, The capacity retention rate is 87%, and the degree of decline is small.
  • Lithium-ion lithium ion conductor Li 7 La 3 Zr 2 O 12 was selected as the solid electrolyte, and LiFePO 4 was used as the positive electrode material.
  • the solid electrolyte precursor powder was weighed according to the mass ratio of the solid electrolyte and the positive electrode material of 20:80 (lithium acetate: barium acetate) : Zirconium acetate is weighed according to the Li 7 La 3 Zr 2 O 12 stoichiometric ratio) and LiFePO 4 powder.
  • the mixed powder was ball milled using a planetary ball mill at a speed of 400 r/min and ball milled for 24 hours.
  • the ball-milled mixed powder is transferred to Al 2 O 3 crucible, and the crucible is placed in a muffle furnace, first heated to 900 ° C at 5 ° C / min, held at 900 ° C for 8 h and then heated to 1125 ° C and then at 1125 After heating at ° C for 12 h, a composite positive electrode material powder having a particle diameter of 100 nm was obtained.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 10 g of the mixture, and the mixture was dispersed in 5 g of NMP.
  • the mixture was uniformly stirred by a vacuum planetary mixer to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil having a thickness of 18 ⁇ m to a coating thickness of 60 ⁇ m. Further, drying was carried out in a vacuum oven at 80 ° C for 24 hours, and the dried electrode sheet was rolled (pressure controlled at 5 MPa), and the solid electrolyte composite positive electrode sheet was obtained by slitting.
  • the negative electrode slurry was obtained, and the negative electrode slurry was applied on a copper foil having a thickness of 12 ⁇ m to a coating thickness of 65 ⁇ m.
  • the mixture was further dried in a vacuum oven at 80 ° C for 24 hours, rolled (pressure controlled at 5 MPa), and slit-cut to obtain a negative electrode sheet.
  • the obtained positive and negative electrode sheets were laminated and assembled with a Li 7 La 3 Zr 2 O 12 solid electrolyte to obtain a solid lithium ion battery.
  • the solid-state lithium ion battery was subjected to charge and discharge cycle test at 25 ° C, 0.5 C charge 1 C discharge, charge and discharge cut-off voltage 3.7 V-2.2 V, and the results showed that the first discharge specific capacity was 118 mAh / g, after 100 cycles, The capacity retention rate is 87%, and the degree of decline is small.
  • Lithium cobaltate was used as the electrode active material, and NASICON lithium ion conductor LiTi 2 (PO4) 3 was used as the solid electrolyte.
  • Lithium cobaltate and LiTi 2 (PO 4 ) 3 were first ball milled uniformly in a planetary ball mill (rotation speed 400 r/min, ball milling 24 h).
  • the mixed powder after the ball milling was uniformly transferred to Al 2 O 3 crucible, the crucible was placed in a muffle furnace, and the temperature was raised to 600 ° C at 5 ° C / min, and the composite powder was obtained by holding at 600 ° C for 12 h.
  • the composite powder was then ball milled with a weighed amount of Fe(III) 4 [Fe(II)(CN) 6 ] 3 ⁇ 14H 2 O (rotation speed 400 r/min, ball milling for 24 h). Finally, the mixed powder after the ball milling was uniform was kept in an oven at 150 ° C for 12 hours to obtain a composite positive electrode material having a particle diameter of 100 nm.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 0.65 g of a mixture, which was dispersed in 0.32 g of NMP solvent.
  • the mixture was thoroughly stirred with a vacuum planetary mixer to obtain a positive electrode slurry.
  • the slurry was coated on an aluminum foil (thickness 65 ⁇ m) to a thickness of 100 ⁇ m. After drying in an oven at 80 ° C for 24 hours, the dried electrode sheets were rolled (pressure controlled at 5 MPa), and the positive electrode sheets were obtained by slitting.
  • a lithium metal plate was used as a negative electrode sheet, and the obtained positive electrode sheet and negative electrode sheet were laminated with LiTi 2 (PO 4 ) 3 as a solid electrolyte, and assembled into a battery to obtain a solid lithium ion battery.
  • the obtained solid-state lithium ion battery was charged and discharged at 25 ° C and 0.2 C, and the first discharge specific capacity was 127 mAh/g, which was higher than that of the general lithium cobaltate positive electrode solid battery. After 50 cycles of 0.2 C charge and discharge cycle, the capacity retention rate was 84%.
  • Lithium cobaltate was used as the electrode active material, and garnet-type lithium ion conductor Li 7 La 3 Zr 2 O 12 was used as the solid electrolyte, and bismuth hexafluorene (DBHQ) was selected as the organic additive material.
  • DBHQ bismuth hexafluorene
  • Lithium cobaltate and Li 7 La 3 Zr 2 O 12 were first ball milled uniformly in a planetary ball mill (rotation speed 400 r/min, ball milling 24 h). The mixed powder after the ball milling was uniformly transferred to Al 2 O 3 crucible, and the crucible was placed in a muffle furnace, and the temperature was raised to 1125 ° C at 5 ° C / min, and the composite powder was obtained by holding at 1125 ° C for 12 h.
  • the composite powder was then ball milled with a weighed bismuthene hexafluorene (rotation speed 400 r/min, ball milling for 24 h). Finally, the ball-milled mixed powder was incubated in an oven at 150 ° C for 12 h to obtain a composite positive electrode material having a particle diameter of 100 nm.
  • the composite positive electrode material, Super P, KS-6 and PVDF were mixed to obtain 0.65 g of a mixture, which was dispersed in 0.32 g of NMP solvent.
  • the mixture was thoroughly stirred with a vacuum planetary mixer to obtain a positive electrode slurry.
  • the slurry was coated on an aluminum foil (thickness 65 ⁇ m) to a thickness of 100 ⁇ m. After drying in an oven at 80 ° C for 24 hours, the positive electrode sheets were obtained by slitting.
  • a lithium metal sheet was used as a negative electrode sheet, and the obtained positive electrode sheet and negative electrode sheet were laminated with Li 7 La 3 Zr 2 O 12 as a solid electrolyte, and assembled into a battery to obtain a solid lithium ion battery.
  • the obtained solid-state lithium ion battery was charged and discharged at 25 ° C and 0.2 C, and the first discharge specific capacity was 130 mAh/g, which was higher than that of the general lithium cobaltate positive electrode solid battery. After 50 weeks of the 0.2 C charge and discharge cycle, the capacity retention rate was 89%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte sur un matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et sur son procédé de préparation, ledit matériau comprenant un matériau actif d'électrode positive composite, un électrolyte solide, et un additif de composé organique, le rapport pondéral entre le matériau actif d'électrode positive, l'électrolyte solide et l'additif de composé organique étant de 80~88:5~15:2~8. Une batterie préparée à l'aide du matériau d'électrode positive composite dispose d'une densité d'énergie améliorée. Le procédé de préparation du matériau d'électrode positive composite permet de réduire la résistance d'interface entre l'électrolyte solide et le matériau d'électrode positive. Lorsque le matériau d'électrode positive composite obtenu à l'aide du procédé de préparation du matériau d'électrode positive composite est utilisé dans la préparation d'une batterie au lithium-ion à semi-conducteur, une ligne de production d'électrodes de batterie au lithium-ion à l'état liquide classiques ne nécessite pas de modification, ce qui permet de réduire considérablement les coûts de mise à niveau de matériel nécessaires à la mise à niveau d'une ligne de production de batteries au lithium-ion à l'état liquide en vue de la préparation de batteries au lithium-ion à semi-conducteur.
PCT/CN2018/073234 2017-02-09 2018-01-18 Matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et son procédé de préparation Ceased WO2018145565A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201710072193.5A CN107017388A (zh) 2017-02-09 2017-02-09 一种用于固态锂离子电池的复合正极材料的制备方法
CN201710070715.8 2017-02-09
CN201710070715.8A CN107017387A (zh) 2017-02-09 2017-02-09 一种用于固态锂离子电池的复合正极材料及其制备方法
CN201710072193.5 2017-02-09

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013069083A1 (fr) * 2011-11-07 2013-05-16 トヨタ自動車株式会社 Batterie entièrement solide
CN103956458A (zh) * 2014-04-29 2014-07-30 清华大学 一种锂离子电池复合正极及其制备方法与在全固态电池中的应用
CN104599859A (zh) * 2013-10-30 2015-05-06 张彩欣 锂离子电容器及其制作方法
CN105680091A (zh) * 2016-01-07 2016-06-15 李震祺 一种高性能全固态锂离子电池及其制备方法
CN107017388A (zh) * 2017-02-09 2017-08-04 上海蔚来汽车有限公司 一种用于固态锂离子电池的复合正极材料的制备方法
CN107017387A (zh) * 2017-02-09 2017-08-04 上海蔚来汽车有限公司 一种用于固态锂离子电池的复合正极材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013069083A1 (fr) * 2011-11-07 2013-05-16 トヨタ自動車株式会社 Batterie entièrement solide
CN104599859A (zh) * 2013-10-30 2015-05-06 张彩欣 锂离子电容器及其制作方法
CN103956458A (zh) * 2014-04-29 2014-07-30 清华大学 一种锂离子电池复合正极及其制备方法与在全固态电池中的应用
CN105680091A (zh) * 2016-01-07 2016-06-15 李震祺 一种高性能全固态锂离子电池及其制备方法
CN107017388A (zh) * 2017-02-09 2017-08-04 上海蔚来汽车有限公司 一种用于固态锂离子电池的复合正极材料的制备方法
CN107017387A (zh) * 2017-02-09 2017-08-04 上海蔚来汽车有限公司 一种用于固态锂离子电池的复合正极材料及其制备方法

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