WO2021004274A1 - Papier graphité modifié, son procédé de préparation, et batterie au lithium-ion le contenant - Google Patents

Papier graphité modifié, son procédé de préparation, et batterie au lithium-ion le contenant Download PDF

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WO2021004274A1
WO2021004274A1 PCT/CN2020/097811 CN2020097811W WO2021004274A1 WO 2021004274 A1 WO2021004274 A1 WO 2021004274A1 CN 2020097811 W CN2020097811 W CN 2020097811W WO 2021004274 A1 WO2021004274 A1 WO 2021004274A1
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graphite paper
modified graphite
preparation
lithium ion
lithium
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PCT/CN2020/097811
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Chinese (zh)
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车欢
杜炳林
朱亚真
李宜
高剑锋
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宁德时代新能源科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/24—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Definitions

  • This application relates to the field of battery technology, in particular to a modified graphite paper, its preparation method and a lithium ion battery containing it.
  • Graphite paper is a kind of graphite product made of high-carbon phosphorous flake graphite after chemical treatment, high temperature expansion and rolling. It is the basic material for manufacturing various graphite seals. It has the characteristics of high temperature resistance, corrosion resistance, and good electrical conductivity. It can be used in petroleum, chemical, electronic, toxic, flammable, high-temperature equipment or components, and can also be made into various graphite strips, fillers, gaskets, Composite plates, cylinder gaskets, etc., as a current collector in the direction of new energy, is a more advanced development direction. Because the preparation of traditional graphite paper requires high raw material purity, the pretreatment process is complicated, and the surface of the resulting product is highly hydrophobic. There are often more difficulties in utilization in this direction.
  • CN105977495B discloses a method for preparing graphite paper for lithium ion battery current collectors, in which expanded graphite powder and lithium polyoxometalate are uniformly mixed to form composite graphite powder; composite graphite powder and water are formulated into a composite graphite suspension ; Mix the composite graphite suspension and the hydrohalic acid into a paint, and then apply the paint on the polyolefin film to form a coating; after the coated polyolefin film is dried, the coating is peeled off from the polyolefin film, The peeled coating is the graphite paper.
  • the lithium polyoxometalate used in the method is expensive, and the hydrohalic acid pollutes the environment greatly.
  • the preparation process requires a polyolefin carrier, which is poor in practicability.
  • CN103427088A discloses a method for preparing graphene paper current collector, wherein graphite oxide is added to a solvent to prepare a graphite oxide suspension; the graphite oxide suspension is ultrasonically stirred to obtain a uniformly dispersed graphene oxide suspension; The graphene oxide suspension is mixed with the hydrazine hydrate solution and reacted to obtain a graphene suspension; the graphene suspension is vacuum filtered by a microporous filter membrane, the filter cake is dried, and then the filter cake is removed from the filter membrane The graphene paper is obtained after the upper peeling; and the graphene paper is reduced in an atmosphere of a reducing gas to obtain a graphene paper current collector.
  • the raw material used in this method is graphite oxide, which is costly, and the product preparation method is suction filtration and stripping, which is not industrialized.
  • the purpose of this application is to provide a modified graphite paper, a method for preparing modified graphite paper, and a lithium ion battery containing the modified graphite paper.
  • a lithium ion battery current collector When used as a lithium ion battery current collector, it can effectively improve the charge and discharge efficiency and energy density of the lithium ion battery.
  • a modified graphite paper is provided, the raw material of which includes graphite recovered from a lithium ion battery, and the carbon content of the modified graphite paper is 96%-99.98%, Preferably it is 98%-99.5%.
  • this application provides a method for preparing modified graphite paper, including:
  • the particles are subjected to hot melt rolling treatment, sintering and cold pressing treatment to obtain the modified graphite paper.
  • the third aspect of the present application provides a current collector, which includes the modified graphite paper described in the first aspect of the present application or the modified graphite paper obtained by the preparation method described in the second aspect of the present application.
  • the fourth aspect of the present application provides a lithium ion battery, which includes the current collector described in the third aspect of the present application.
  • a fifth aspect of the present application provides a device, which includes the lithium ion battery according to the fourth aspect of the present invention.
  • the modified graphite paper prepared from the electrochemically cycled graphite recovered from the used lithium battery current collector has better affinity as the lithium battery current collector.
  • the interlayer spacing increases, and the edge
  • the surface functional groups of carbon atoms are grafted and activated, and no special treatment is required.
  • the surface is rich in hydroxyl, carboxyl, carbonyl and other functional groups, which can greatly reduce the surface energy and facilitate the spreading and wetting of the slurry on the surface.
  • the angle (contact angle) is small.
  • the surface of the highly active current collector can be complexed and bonded with active materials and binders, which is beneficial to reduce the interface contact resistance, especially for water-based active materials coating, which has better interfacial adhesion, especially for graphite , Silicon-carbon and other homologous materials have better affinity, which is beneficial to the improvement of the battery's long-cycle capacity, and by controlling a series of reaction conditions such as temperature and pressure, graphite with higher purity and various excellent chemical properties can be obtained. Paper is more conducive to the improvement of the electrochemical performance of lithium-ion batteries. At the same time, the problem of graphite negative electrode material in the cascade utilization and recycling of lithium ion batteries is solved, and the preparation cost of graphite paper is reduced.
  • FIG. 1 is a schematic diagram of an embodiment of the lithium ion battery of the present application.
  • FIG. 2 is an exploded schematic diagram of an embodiment of the lithium ion battery of the present application.
  • Fig. 3 is a schematic diagram of an embodiment of a battery module.
  • Fig. 4 is a schematic diagram of an embodiment of a battery pack.
  • Fig. 5 is an exploded view of Fig. 4.
  • FIG. 6 is a schematic diagram of an embodiment of a device in which the lithium ion battery of the present application is used as a power source.
  • any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and any upper limit may be combined with any other upper limit to form an unspecified range.
  • each individually disclosed point or single value can be used as a lower limit or upper limit in combination with any other point or single value or with other lower or upper limits to form an unspecified range.
  • the modified graphite paper of the first aspect of the application and the method for preparing the modified graphite paper of the first aspect of the application are described in detail in the following.
  • the third aspect of the application adopts the method of the first aspect of the application.
  • Graphite paper has low density and high strength. Compared with the copper and aluminum foil of the current collector for lithium-ion batteries, it can greatly reduce the weight of the battery, thereby improving the quality and energy density of the battery.
  • the thermal conductivity of graphite paper is higher than that of metal current collectors. Because graphite has in-plane ⁇ bonds, it can provide free electrons similar to metals. During the charging and discharging process of the battery, the heat of the battery can be more uniform. Distribution, thereby reducing the polarization of the battery, improving the uniformity of heat and current distribution, and improving safety performance.
  • non-metallic graphite current collectors can greatly reduce the resource and energy consumption of the lithium battery industry compared to metal current collectors.
  • the raw material of the modified graphite paper includes graphite recovered from lithium ion batteries, and the carbon content of the modified graphite paper is 96%-99.98%, Preferably it is 98%-99.5%.
  • graphite recovered from used lithium ion batteries is used as the main raw material of modified graphite paper.
  • the inventor of the present application found that the carbon content of the modified graphite paper is very important for whether the modified graphite paper can be used in battery current collectors.
  • the carbon content in the modified graphite paper will affect the thermal conductivity, wetting angle, and The calendering ability affects the first Coulomb efficiency and long cycle capacity of the graphite paper capacitor.
  • the carbon content in the modified graphite paper is 96%-99.98%, its first coulombic efficiency and long-cycle capacity can be effectively improved.
  • the low carbon content in graphite paper means that the content of impurities such as ash is high. The above impurities will reduce the electrical and thermal conductivity of the product. Therefore, when the carbon content in modified graphite paper is higher than 98%, its first coulombic efficiency and long-term cycle capacity can be Get further improvement.
  • the carbon content is too high, it will damage the ductility of the modified graphite paper, which is not suitable for its production and application as a battery current collector. Therefore, the carbon content of the modified graphite paper is controlled below 99.5%.
  • the degree of graphitization of modified graphite paper affects the electrochemical performance of lithium-ion batteries. This is because the degree of graphitization can affect the electrical conductivity, in-plane thermal diffusion rate, wetting angle, and calendering of the modified graphite paper. Capability; In turn, it affects the first Coulomb efficiency and long cycle capability of the graphite paper capacitor.
  • the graphitization degree of the modified graphite paper is 88%-99%, its first coulombic efficiency and long-cycle capacity can be effectively improved. Therefore, when the degree of graphitization in the modified graphite paper is above 92%, its first coulombic efficiency and long cycle capability can be further improved.
  • the graphitization degree of the modified graphite paper is 88%-99%, preferably 92%-99%.
  • modified graphite paper affects the electrochemical performance of lithium-ion batteries. This is because the thermal conductivity of modified graphite paper can affect the internal polarization of the battery and affect the rate and cycle life. The thermal conductivity not only affects the polarization inside the graphite paper, but also affects the heat diffusion of the lithium-ion battery.
  • the planar thermal conductivity of the graphite paper affects the heat distribution on the plane of the pole piece, making the battery less prone to local hot spots and causing safety problems.
  • the thermal conductivity in the thickness direction can make the heat of the battery be quickly discharged through the current collector and the battery shell in time, so that the heat of the battery can be quickly discharged, and reduce the problem of thermal runaway caused by the excessive internal temperature of the battery.
  • the in-plane thermal conductivity of the modified graphite paper is 180-580 W/(m.K), preferably 200-580 W/(m.K).
  • the thickness direction thermal conductivity of the modified graphite paper is 4-10 W/(m.K); preferably 5-10 W/(m.K).
  • the thickness of the modified graphite paper affects the electrochemical thermal conductivity of the lithium ion battery, and further affects the electrochemical performance of the lithium ion battery.
  • the thickness of graphite paper is too low to affect its calendering ability, while the thickness of graphite paper is too high to lose its advantage as a current collector. Therefore, according to the embodiment of the modified graphite paper of the present application, the thickness of the modified graphite paper is 4.5-90um, preferably 5-35um.
  • this application provides a method for preparing modified graphite paper, including the following steps:
  • the particles are subjected to hot melt rolling treatment, sintering and cold pressing treatment to obtain the modified graphite paper.
  • step (2) acid treatment can remove metal impurities, and carbon will also be oxidized to generate hydrophilic functional groups such as hydroxyl, carbonyl, and carboxyl groups, which is conducive to the infiltration and coating of later active materials.
  • hydrophilic functional groups such as hydroxyl, carbonyl, and carboxyl groups
  • the acid treatment in step (2) is performed under heating conditions.
  • Heating time (acidification time) will affect the structural rearrangement of the carbon itself and the interlayer spacing, thus affecting the graphitization degree of the modified graphite paper, which in turn affects the thermal conductivity of the modified graphite paper and the electrochemical performance of the lithium ion battery .
  • the acid solution is one or more of hydrochloric acid, nitric acid, sulfuric acid, and hydrofluoric acid solutions.
  • the heating time of the acid treatment is 60-300 min, preferably 60-120 min.
  • the heating temperature of the acid treatment in step (2) is 40-85°C.
  • the acid treatment in step (2) is performed under ultrasound conditions, and the power of the ultrasound is preferably 20-50KHZ.
  • the purpose of adding thermoplastic materials in step (3) is to provide cohesiveness, which is conducive to product compression molding.
  • the thermoplastic material is selected from one or more of phenolic resin, polyethylene, polypropylene, epoxy resin, and polyimide.
  • the mass ratio of the second precursor to the thermoplastic material is 5-8:2-5, preferably 6-8:2-4.
  • the inventor of the present application found that in the process of hot melt calendering, sintering, and cold pressing of the mixed particles, the selection of the sintering temperature and the selection of the cold pressing pressure have a greater impact on the properties of the modified graphite paper.
  • the sintering temperature determines the degree of carbonization and decomposition of the thermoplastic material and its combination with the aggregate graphite, and therefore affects the carbon content of the modified graphite paper.
  • a lower temperature will lead to incomplete pyrolysis of organic matter in the modified graphite paper, thereby reducing the carbon content , Resulting in a decrease in the properties (thermal conductivity, electrical conductivity) of the modified graphite paper; but too high temperature will reduce the plasticity of the modified graphite paper and affect the molding of the modified graphite paper.
  • the sintering temperature is 800-1300°C, preferably 950°C-1200°C.
  • the inventor of the present application found that cold pressing pressure has an important effect on the molding of modified graphite paper, which is reflected in its influence on the thickness and surface finish of the modified graphite paper; too high pressure will lead to excessive internal stress of the modified graphite paper , So that the modified graphite paper will undergo stress release in the later stage to cause deformation and rebound; too low pressure will not reach the expected thickness, density and other indicators, which will affect the performance from the physical structure.
  • the pressure of the cold press is 15-60T, preferably 22-50T, and it is worth noting that the T means ton.
  • the processing temperature of the cold pressing is 25-55°C.
  • the processing temperature of hot melt calendering is 400-700°C, and the pressure is 15-60T.
  • the protective atmosphere for the sintering is one or more of nitrogen, argon, and helium.
  • the preparation method of the modified graphite paper may include the following steps:
  • the first precursor is added to a strong acid solution with a pH ⁇ 2, heating and ultrasonic treatment are performed at the same time, and the acidified product is washed with deionized water until the pH of the eluate is >5 to obtain a second precursor;
  • the second precursor is mixed with the thermoplastic material, it is crushed into mixed particles with a particle size D50 of 8-30 um, and the mixed particles are subjected to hot melt calendering, sintering and cold pressing to obtain the modified graphite paper.
  • the current collector of the third aspect of the present invention which includes the modified graphite paper described in the first aspect of the present invention and/or the modified graphite paper obtained by the preparation method described in the second aspect of the present invention.
  • the current collector may further include a negative active material, a conductive agent, and the like.
  • the lithium ion battery of the fourth aspect includes a positive pole piece, a negative pole piece, and an electrolyte.
  • active ions are inserted and extracted back and forth between the positive pole piece and the negative pole piece.
  • the electrolyte conducts ions between the positive pole piece and the negative pole piece.
  • the negative pole piece includes a negative electrode current collector and a negative electrode film layer.
  • the inventor has discovered through research that when the negative pole piece of a lithium ion battery adopts the modified graphite paper of the first aspect of the present application, it can ensure that the battery has both excellent fast charging performance and cycle performance.
  • DV10, DV50, and Dv90 of the negative electrode active material are all known meanings in the art, and can be tested by methods known in the art.
  • a laser diffraction particle size distribution measuring instrument such as Malvern Mastersizer 3000 laser particle size analyzer.
  • Dv10 refers to the particle size when the cumulative volume percentage of material particles or powder reaches 10%
  • Dv50 refers to the particle size when the cumulative volume percentage of material particles or powder reaches 50%
  • Dv90 refers to the cumulative volume of material particles or powder The particle size when the percentage reaches 90%.
  • test sample of the negative electrode active material can be sampled and tested before coating, or can be sampled and tested from the negative electrode film after cold pressing.
  • the sampling can be carried out as follows: arbitrarily select a cold-pressed negative electrode film and sample the negative electrode active material (a blade can be selected) Scrape sampling), put the collected negative active material in deionized water, filter the negative active material, dry, and then burn the dried negative active material at 400°C for 2h to remove the binding And conductive carbon to obtain the test sample of the negative electrode active material.
  • the negative active materials of the present application can all be obtained through commercial channels.
  • the negative electrode film layer may be arranged on one surface of the negative electrode current collector, or may be arranged on both surfaces of the negative electrode current collector at the same time.
  • the parameters of each negative electrode film (such as film thickness, areal density, etc.) given in this application all refer to the parameter range of a single-sided film.
  • the film layer parameters on any one of the surfaces meet the requirements of the present application, which is considered to fall within the protection scope of the present application.
  • the ranges of film thickness, areal density and the like mentioned in this application all refer to film parameters after cold compaction and used to assemble batteries.
  • the negative electrode film layer usually contains a negative electrode active material, an optional binder, an optional conductive agent, and other optional auxiliary agents, which are usually obtained by coating and drying the negative electrode film slurry.
  • the negative electrode film slurry coating is usually formed by dispersing the negative electrode active material and optional conductive agent and binder in a solvent and stirring uniformly.
  • the solvent can be N-methylpyrrolidone (NMP) or deionized water, for example.
  • NMP N-methylpyrrolidone
  • Other optional additives can be, for example, thickening and dispersing agents (such as sodium carboxymethyl cellulose CMC-Na), PTC thermistor materials, and the like.
  • the conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the binder may include styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer One or more of (EVA), polyvinyl alcohol (PVA) and polyvinyl butyral (PVB).
  • SBR styrene-butadiene rubber
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • EVA ethylene-vinyl acetate copolymer
  • EVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • the negative electrode active material may also optionally include a certain amount of other commonly used negative electrode active materials, such as soft carbon, hard carbon, silicon-based materials, One or more of tin-based materials and lithium titanate.
  • the silicon-based material can be selected from one or more of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, and silicon alloys.
  • the tin-based material can be selected from one or more of elemental tin, tin oxide compounds, and tin alloys. The preparation methods of these materials are well known and can be obtained commercially. Those skilled in the art can make an appropriate choice according to the actual use environment.
  • the negative electrode sheet does not exclude other additional functional layers besides the negative electrode film layer described above.
  • the negative pole piece of the present application may further include a conductive coating (for example, composed of a conductive agent and a binder) disposed between the negative current collector and the first film layer.
  • the negative pole piece of the present application may further include a protective layer provided on the surface of the second film layer.
  • the positive pole piece includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector and including a positive electrode active material.
  • the positive electrode current collector has two opposite surfaces in the thickness direction of the positive electrode current collector, and the positive electrode membrane may be laminated on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used.
  • the composite current collector can be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer substrate.
  • the positive electrode active material can be a positive electrode active material for lithium ion batteries known in the art.
  • the positive electrode active material may include one or more of lithium transition metal oxides, lithium-containing phosphates with an olivine structure, and their respective modified compounds.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide One or more of lithium nickel cobalt aluminum oxide and its modified compounds.
  • lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate, lithium iron phosphate and carbon composite material, lithium manganese phosphate, lithium manganese phosphate and carbon composite material, lithium iron manganese phosphate, lithium iron manganese phosphate One or more of composite materials with carbon and its modified compounds.
  • the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for lithium ion batteries can also be used.
  • the positive electrode active material may include one or more of the lithium transition metal oxide and its modified compounds shown in Formula 1.
  • M is selected from Mn, Al, Zr
  • Zn is selected from Mn, Al, Zr
  • Zn is selected from Mn, Al, Zr
  • the modification compound of each of the above-mentioned materials may be doping modification and/or surface coating modification on the material.
  • the electrolyte conducts ions between the positive pole piece and the negative pole piece.
  • the electrolyte may be selected from at least one of solid electrolytes and liquid electrolytes (ie, electrolytes).
  • an electrolyte is used as the electrolyte.
  • the electrolyte includes electrolyte salt and solvent.
  • the electrolyte salt may be selected from LiPF 6 (lithium hexafluorophosphate), LiBF 4 (lithium tetrafluoroborate), LiClO 4 (lithium perchlorate), LiAsF 6 (lithium hexafluoroarsenate), LiFSI (bisfluorosulfonate) Lithium imide), LiTFSI (lithium bistrifluoromethanesulfonimide), LiTFS (lithium trifluoromethanesulfonate), LiDFOB (lithium difluorooxalate borate), LiBOB (lithium dioxalate borate), LiPO2F 2 (two One or more of lithium fluorophosphate), LiDFOP (lithium difluorodioxalate phosphate) and LiTFOP (lithium tetrafluorooxalate phosphate).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • the solvent may be selected from ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate Ester (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB) , Ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS) and diethyl sulfone (ESE) one
  • the electrolyte may also optionally include additives.
  • the additives can include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performance of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature performance, and those that improve battery low-temperature performance. Additives etc.
  • Lithium-ion batteries that use electrolytes and some lithium-ion batteries that use solid electrolytes also include separators.
  • the isolation film is arranged between the positive pole piece and the negative pole piece to play a role of isolation.
  • any well-known porous structure isolation membrane with good chemical and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from one or more of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multilayer composite film. When the isolation film is a multilayer composite film, the materials of each layer can be the same or different.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • the lithium ion battery may include an outer packaging.
  • the outer package can be used to package the electrode assembly and electrolyte.
  • the outer packaging of the lithium ion battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the lithium ion battery can also be a soft bag, such as a pouch type soft bag.
  • the material of the soft bag can be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
  • Fig. 1 shows a lithium ion battery 5 having a square structure as an example.
  • the outer package may include a housing 51 and a cover 53.
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the housing 51 has an opening communicating with the containing cavity, and a cover plate 53 can cover the opening to close the containing cavity.
  • the positive pole piece, the negative pole piece and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the lithium ion battery 5 can be one or several, which can be adjusted according to requirements.
  • lithium ion batteries can be assembled into battery modules, and the number of lithium ion batteries contained in the battery modules can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • FIG. 3 is a battery module 4 as an example.
  • a plurality of lithium ion batteries 5 may be arranged in order along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of lithium ion batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of lithium ion batteries 5 are accommodated in the accommodation space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the positive pole piece of the present application can be prepared as follows: the positive electrode active material, optional conductive agent (such as carbon black and other carbon materials), binder (such as PVDF), etc. are mixed and dispersed in a solvent (such as NMP) In the process, after being evenly stirred, it is coated on the positive electrode current collector and dried to obtain the positive electrode pole piece.
  • a solvent such as NMP
  • Metal foils such as aluminum foil or porous metal plates can be used as the positive electrode current collector.
  • the positive electrode tab can be prepared in the uncoated area of the positive electrode current collector by punching or laser die cutting.
  • the positive pole piece, the isolation film, and the negative pole piece can be stacked in order, so that the isolation film is located between the positive and negative pole pieces for isolation, and then the electrode assembly is obtained through the winding (or lamination) process;
  • the electrode assembly is placed in the outer package, and the electrolyte is injected after drying, and the lithium-ion battery is obtained through the processes of vacuum packaging, standing, forming, and shaping.
  • the fourth aspect of the application provides an apparatus.
  • the device includes the lithium ion battery of the third aspect of the present application.
  • the lithium ion battery can be used as a power source of the device, and can also be used as an energy storage unit of the device.
  • the device in this application uses the lithium ion battery provided in this application, and therefore has at least the same advantages as the lithium ion battery.
  • the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • mobile devices such as mobile phones, laptop computers, etc.
  • electric vehicles such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.
  • electric trains ships and satellites, energy storage systems, etc.
  • the device can select a lithium ion battery, battery module or battery pack according to its usage requirements.
  • Figure 6 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • battery packs or battery modules can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device usually requires light and thin, and can use lithium-ion batteries as a power source.
  • the modified graphite paper and its lithium ion battery of Examples 1-13 were prepared according to the following method.
  • the second precursor is mixed with the thermoplastic material, it is pulverized into mixed particles with a particle size D50 of 10 um, and the mixed particles are subjected to hot melt calendering, sintering, and cold pressing to obtain the modified graphite paper.
  • the thermoplastic material is a phenolic resin; the mass ratio of the second precursor to the thermoplastic material is 8:2; the sintering temperature adopts the temperature shown in Examples 1-13 in Table 1, and the sintering time is 14 hours.
  • the hot melt calendering treatment temperature is 430°C and the pressure is 30T; the cold pressing treatment temperature is 45°C, and the pressure adopts the cold pressing pressure shown in Example 1-13 of Table 1.
  • the button battery is prepared according to the following method:
  • pole piece the active material, conductive agent (super P carbon black), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR): deionized water according to the mass ratio of 90:2.5:2.5:5: After stirring at a rate of 100 and a speed of 800 r/min for 12 hours, it was coated on the modified graphite paper obtained in Examples 1-13, and the battery pole pieces were obtained after rolling, slitting, and baking.
  • conductive agent super P carbon black
  • CMC sodium carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • Electrolyte preparation In an argon atmosphere glove box with a water content of ⁇ 10ppm, mix ethylene carbonate (EC): dimethyl carbonate (DMC): ethyl methyl carbonate (with a mass ratio of 25:20:55) EMC) is uniformly mixed to obtain a mixed solvent, and then fully dried lithium hexafluorophosphate (LiPF 6 ) is dissolved in the above mixed solvent, and after uniform stirring, an electrolyte is obtained. Among them, the concentration of lithium hexafluorophosphate (LiPF 6 ) is 1.2 mol/L.
  • the isolation film adopts polyethylene film.
  • Test equipment muffle furnace, electric heating constant temperature drying oven, analytical balance, crucible tongs, dryer, porcelain
  • Test procedure along the length of the material to be inspected, take samples (clean surface, no less than 4g) on the left, middle and right parts of the material, cut into pieces, and mix evenly; take the mixed sample (not less than 20g) and place Put it in an electric heating constant temperature drying oven at 105-110°C for 1 hour, and place it in a desiccator to cool for 30 minutes; accurately weigh 1g of the dried sample in a porcelain dish that has been burned to a constant weight, accurate to ⁇ 0.0002g; Put the porcelain dish with the sample into the muffle furnace and burn it at 800-850°C until there are no black spots; remove the porcelain dish from the furnace, cool it in the air for 5-10 minutes, and then put it in a desiccator to cool to Weigh at room temperature and repeat this step until the error of the two weighing values is less than 0.0005g.
  • carbon content 1-(the last heavy weight-the weight of the porcelain vessel) / sample weight * 100%.
  • Test equipment X-ray diffractometer, agate mortar, sample carrier, standard silicon, 200 mesh standard sieve
  • Test procedure Take a clean sample (not less than 20g), cut it into pieces, grind it with an agate mortar, let it all pass through a 200-mesh standard sieve, use this powder as a sample, and mix it with the standard silicon powder at a ratio of 1:0.2. After mixing, the sample powder is loaded into the sample carrier, smoothed, and tested for its graphitization degree with an X-ray diffractometer.
  • Thickness using ten-thousand-meter test
  • Test procedure Take a clean sample, measure its thickness with a micrometer, test more than 10 data in the horizontal and vertical directions, and take the average value.
  • Test equipment micrometer, vernier caliper, nickel-chromium-nickel-silicon armored thermocouple, precision digital temperature indicator, DC digital voltmeter, fixed value shunt, split heat-proof furnace, precision temperature controller, DC power supply.
  • Test procedure Take a clean sample and cut it into a sample with a width of 16mm ⁇ 1mm and a length of 190 ⁇ 1mm. Use a DC power supply to heat both ends of the sample. When the sample is passed through the DC, the heat generated is mainly conducted along the longitudinal ends of the sample After reaching the thermally stable state, it is considered that there is a one-dimensional longitudinal heat flow on the sample. Use the equipment to correct the heat exchange between the sample and the lateral environment, and record the temperature of each point and the current passed into the sample, the working interval voltage, repeat 3. -Take the average of 5 times to calculate the thermal conductivity.
  • First discharge capacity use a test cabinet to measure the lithium-ion battery, discharge at a rate of 0.1C, discharge until the voltage is 0.05V, and record the first discharge capacity.
  • First charge capacity use a test cabinet to measure the lithium-ion battery, discharge at a rate of 0.1C, discharge until the voltage is 0.05V, charge at a rate of 0.05C, charge until the voltage is 2V, and record the charge and discharge capacity;
  • the lithium ion battery containing the modified graphite paper prepared in Examples 1-13 has a higher initial charge capacity and a higher initial charge capacity than the commercially available lithium ion batteries in Comparative Examples 1-3.
  • Efficiency It shows that the use of modified graphite paper to prepare lithium ion batteries improves the charge and discharge efficiency and energy density of lithium ion batteries, and the battery performance has been greatly improved.
  • the sintering temperature affects the carbon content of the modified graphite paper, which in turn affects the thermal conductivity of the modified graphite paper and the electrochemical performance of the lithium ion battery.
  • Reasonably control the sintering temperature Effectively improve the carbon content of graphite paper, resulting in better electrochemical performance.
  • the cold pressing pressure affects the thickness of the modified graphite paper.
  • changing the cold pressing pressure can effectively control the graphite under the condition of a certain feed.
  • the thickness of the paper and the thickness of the graphite paper are controlled within an appropriate range, which can better improve the electrochemical performance of the lithium-ion battery, mainly because the thickness of the graphite paper affects the thermal conductivity and electrical conductivity of the modified graphite paper to further enhance the lithium The electrochemical performance of ion batteries.
  • the heating time (acidification time) mainly affects the graphitization degree of the modified graphite paper, and the graphitization degree of the graphite paper affects the thermal conductivity and electrical conductivity of the modified graphite paper This further affects the electrochemical performance of lithium-ion batteries.

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Abstract

L'invention concerne un papier graphité modifié, un procédé de préparation du papier graphité modifié, un collecteur de courant et une batterie au lithium-ion. Les matières premières du papier graphité modifié comprennent du graphite récupéré à partir de batteries au lithium-ion. La teneur en carbone du papier graphité modifié est de 96 % à 99,98 %, de préférence de 98 % à 99,5 %. Lorsque le papier graphité modifié est utilisé comme collecteur de courant d'une batterie au lithium-ion, l'efficacité de charge et de décharge et la densité d'énergie de la batterie au lithium-ion peuvent être efficacement améliorées.
PCT/CN2020/097811 2019-07-08 2020-06-23 Papier graphité modifié, son procédé de préparation, et batterie au lithium-ion le contenant WO2021004274A1 (fr)

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