CN112599760A - Metal type negative electrode slurry, negative electrode plate and secondary battery - Google Patents
Metal type negative electrode slurry, negative electrode plate and secondary battery Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 89
- 239000002184 metal Substances 0.000 title claims abstract description 89
- 239000011267 electrode slurry Substances 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000007773 negative electrode material Substances 0.000 claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 57
- 239000006258 conductive agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 16
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- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- -1 graphite, natural modified graphite Chemical class 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000006182 cathode active material Substances 0.000 claims description 10
- 239000006183 anode active material Substances 0.000 claims description 8
- 239000006256 anode slurry Substances 0.000 claims description 7
- 239000006257 cathode slurry Substances 0.000 claims description 7
- 239000002003 electrode paste Substances 0.000 claims description 7
- 239000007770 graphite material Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 9
- 150000004706 metal oxides Chemical class 0.000 abstract description 9
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- 238000007599 discharging Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
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- 239000011888 foil Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
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- 238000002360 preparation method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
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- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
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- 239000007789 gas Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
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- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000000498 ball milling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
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- 239000004952 Polyamide Substances 0.000 description 1
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- 229910001245 Sb alloy Inorganic materials 0.000 description 1
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- 239000002140 antimony alloy Substances 0.000 description 1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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Abstract
The invention discloses metal type negative electrode slurry, a negative electrode plate and a secondary battery, and relates to the technical field of lithium batteries. The negative electrode slurry comprises 55-95% of carbon negative electrode active materials and 1-40% of high-capacity metal negative electrode active materials in percentage by mass; the particle size of the carbon-based negative electrode active material is larger than that of the high-capacity metal negative electrode active material. According to the invention, by utilizing the characteristic that gaps exist due to different particle sizes of the materials, other components in the slurry are uniformly dispersed among the carbon negative electrode material particles. The slurry is coated on a negative current collector to prepare a negative pole piece, so that the metal particles or metal oxide particles have good conductivity, and the gaps formed by stacking the carbon negative poles enable the metal particles or metal oxide particles dispersed in the gaps to have a certain deformation space when the volume of the metal particles or metal oxide particles is changed during charging and discharging, so that the damage of stress strain caused by the volume change is reduced, and the battery performance is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to metal type negative electrode slurry, a negative electrode plate and a secondary battery.
Background
In recent two thirty years, researchers in the field of new energy research have conducted extensive and intensive research on alloyed negative electrode materials, and the development of the alloyed negative electrode materials towards the application direction is promoted. However, after many years of research, the current alloyed negative electrode material is not widely used. Many materials remain in the academic research phase. At present, the most suitable alloying negative electrode material for large-scale application is a silicon-carbon negative electrode material, but the application of the alloying negative electrode material is restricted due to the problems of poor conductivity, volume expansion, poor cycle performance, high cost and the like. Metal alloy negative electrodes, particularly aluminum metal negative electrodes, having excellent conductive properties have attracted considerable attention and have been intensively studied.
For example, the article of 'research on modification of micron-sized spherical aluminum powder as a lithium ion battery negative electrode material' published by leixuefeng et al shows that the capacity of 3 um-grade aluminum powder as a negative electrode material only exerts 103mAh/g, and after the aluminum powder is modified by high-temperature carbon on the surface, the capacity is highest 592mAh, but the first efficiency is lower than 60%, and the capacity retention rate of the optimal battery is lower than 60% after 10 weeks of battery circulation. The existence of a passivation layer on the surface of the aluminum powder prevents the 3um aluminum powder from being directly used as a negative electrode material; the patent CN101937994.A "graphene/aluminum composite negative electrode material of lithium ion battery and preparation method thereof" proposes that the graphene/aluminum composite negative electrode material is prepared by adopting a graphene and metal aluminum powder ball milling mode, the capacity of the material can reach 1100mAh/g, but the cycle is less than 10 weeks, and the capacity is kept lower than 80%. This explains the problem that the conventional metal aluminum powder cannot exert capacity as a negative electrode material, and modification treatment is required, but the conventional modification scheme cannot solve the problem of cycle performance although the conventional modification scheme effectively exerts the capacity of the aluminum powder. CN202010704786.0 composite material, its preparation method and negative electrode, proposes that high-capacity negative electrode materials such as high-capacity aluminum and the like are deposited on the surface of graphite particles, and then deposited or coated with carbon to make a three-layer negative electrode material, so as to improve the gram-capacity and cycle performance of the negative electrode. The design idea is to improve the capacity of the cathode material and the cycle performance of the battery, but the problems of high manufacturing cost, complex process, relatively low proportion of deposited high-capacity active material and the like exist.
At present, research and development are carried out on high-capacity negative electrode materials, particularly on modes of nano-crystallization, surface modification or deposition on the graphite surface of metal aluminum and other series metal materials or metal oxide materials. These methods can improve the performance of the material in terms of capacity, cycle, etc., but all have common problems, such as high manufacturing cost and complicated process.
In a traditional lithium ion battery system, a negative active material mainly adopts a carbon negative material, in particular a graphite negative material. However, with the progress of science and technology, the functions of electronic equipment products are continuously increased and the requirements of customers on the comfort level of experience are continuously improved, and the functions are limited by low gram capacity of the graphite cathode and low lithium intercalation potential, so that the battery products cannot meet the requirements of the market on higher energy density, and the potential safety hazard of the battery is increasingly prominent along with the improvement of the energy density of the battery. Therefore, development of novel high-capacity and high-safety battery materials is actively underway.
The novel cathode material mainly comprises a silicon cathode, a silicon-oxygen cathode, a silicon-carbon cathode, an aluminum cathode, a tin alloy cathode, a tin oxide cathode, an antimony alloy cathode and other cathode materials. The development of these new anode materials is relatively mature, mainly silicon carbon materials and silicon oxygen materials, and has been applied in a small amount. At present, the capacity of a silicon negative electrode material which is applied in a small amount in batches is mainly about 420mAh, but the novel silicon negative electrode material has large volume expansion and poor rate capability. The main reasons for this are that silicon is a semiconductor material, its conductivity is poor, and the volume expansion of the silicon material is large (400% volume change). In addition, silicon or silicon-oxygen materials of the silicon-based anode material need to be manufactured and processed into a nanometer or submicron grade, so that the silicon-based anode material is high in cost and expensive in selling price.
Disclosure of Invention
The invention aims to solve the technical problems that the existing battery using metal aluminum powder as a negative electrode material has poor cycle performance and high manufacturing cost.
In order to solve the above problems, the present invention proposes the following technical solutions:
in a first aspect, the invention provides a metal type cathode slurry, which comprises 55-95% of carbon cathode active material and 1-40% of high-capacity metal cathode active material by mass percentage; the particle size of the carbon-based negative electrode active material is larger than that of the high-capacity metal negative electrode active material.
The high capacity means that the volume of the lithium ion is changed greatly when the lithium ion is deintercalated, and the deintercalated lithium specific capacity is high.
The carbon negative electrode active material D50 is 4-20 um, and the high-capacity metal negative electrode active material D50 is 0.5-10 um.
The further technical scheme is that the high-capacity metal negative active material is selected from one or more of aluminum, germanium, tin, antimony, zinc, germanium oxide, tin oxide, antimony oxide, zinc oxide and copper oxide.
The carbon negative active material is selected from one or more of artificial graphite, natural modified graphite, soft carbon, hard carbon, composite graphite, mesocarbon microbeads and expanded graphite materials.
The technical scheme is that the conductive adhesive further comprises 0-5% of a conductive agent and 0.5% -5% of a binder by mass percentage.
The further technical scheme is that the conductive agent is selected from one or more of acetylene black, carbon black, ketjen black, conductive graphite, carbon fiber, carbon nano wire, carbon nano tube and graphene.
The further technical proposal is that the binder is selected from PVDF and/or modified PVDF.
The invention also provides a method for preparing the metal type cathode slurry, which is characterized in that the binder is beaten into glue solution according to the proportion, the high-capacity metal cathode active material, the conductive agent and the carbon cathode active material are gradually added, and the uniform and stable metal type cathode slurry is obtained after the uniform dispersion.
The invention also provides a metal type negative pole piece, which is obtained by uniformly coating the metal type negative pole slurry obtained by the preparation method on a negative pole current collector and drying.
The negative current collector is an inactive conductive foil current collector, and may be, but is not limited to, a non-porous copper foil, a non-porous nickel foil, a non-porous iron foil, a non-porous stainless steel foil, a porous copper foil, a porous nickel foil, a porous iron foil, a porous stainless steel foil, a copper mesh, a nickel mesh, an iron mesh, a stainless steel mesh, a conductive carbon cloth, and the like.
The specific method for manufacturing the negative electrode plate can also be that the adhesive, the conductive agent and the high-capacity metal negative electrode active material are stirred and dispersed into uniform slurry in a stirring mode, so that the high-capacity metal negative electrode active material is uniformly dispersed in the conductive agent, then the carbon negative electrode material is added and stirred and dispersed to form uniform and stable slurry, so that the high-capacity metal negative electrode active material and the conductive agent are uniformly dispersed among carbon negative electrode material particles, and finally the slurry is coated on two surfaces of the inactive conductive foil current collector.
The invention also provides a secondary battery which comprises the metal type negative pole piece, the positive pole piece, the diaphragm and the electrolyte.
The secondary battery can be manufactured by a conventional processing method.
The positive active material of the positive pole piece is one or two or more of composite materials of lithium iron phosphate, lithium manganese phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium nickelate, lithium titanate, artificial graphite, natural modified graphite, soft carbon, hard carbon, carbon nano tubes, graphene, composite graphite, mesocarbon microbeads, expanded graphite materials and the like.
The diaphragm is a woven film, a non-woven film (non-woven fabric), a microporous film, a composite film and a corresponding ceramic modified film which are made of a polyethylene film, a polypropylene film, polyamide, glass fiber, polyvinylidene fluoride and the like.
Compared with the prior art, the invention can achieve the following technical effects:
the metal type cathode slurry provided by the invention is used for carrying out particle size optimization, proportion optimization and cathode material pulping process optimization on the practical application of the micron-sized high-capacity metal cathode active material with high specific capacity and large volume expansion for the first time. By making the particle size of the carbon negative active material larger than that of the high-capacity metal negative active material, other components in the slurry, such as the conductive agent, can be well dispersed and coated on the surface of the high-capacity metal negative active material particles, and the high-capacity metal negative active material particles and the conductive agent are uniformly dispersed among the carbon negative active material particles. The slurry is coated on a negative current collector to prepare a negative pole piece, so that metal particles or metal oxide particles can be ensured to have good conductivity, and the metal particles or metal oxide active particles are filled in the middle of gaps formed by stacking carbon negative active material particles, so that the stacking density of powder particles is improved. The stacking mode not only effectively utilizes the gaps existing when the carbon negative electrode large particles are stacked, but also ensures that the metal negative electrode active material particles dispersed in the gaps have certain deformation space when the volume changes during charging and discharging due to the gaps formed by stacking the carbon negative electrode active material, reduces the damage of stress strain caused by the volume change, and ensures that the metal particles or the metal oxide particles are in good contact with the carbon negative electrode particles during the charging and discharging processes, thereby ensuring that the conductivity of the whole pole piece is not changed. And the small-particle metal negative active material can carry out lithium intercalation and lithium removal from the particle surface in an all-around way and can embed lithium at a higher potential (more than 0.1V), so that the novel negative material and the secondary battery thereof have the performances of high energy density, high multiplying power, high safety, long cycle and the like. Therefore, the design of the invention fully considers the functions of the negative pole piece and the characteristics of the lithium ions in the process of alloying with the negative active material, and is expected to realize the application of the alloying negative pole material with high specific capacity and large volume expansion in a battery system through the optimization of material matching design and the optimization of pulping process.
Drawings
Fig. 1 is an SEM image of CNT coating on the surface of aluminum powder particles after CNT (carbon nanotube) and aluminum powder are added, stirred and dispersed during the process of preparing the metal-type negative electrode paste according to an embodiment of the present invention;
fig. 2 is an SEM image of the metal-type negative electrode paste according to an embodiment of the present invention, in which CNTs (carbon nanotubes), aluminum powder, and graphite are added, and the mixture is stirred and dispersed;
fig. 3 is a cycle curve diagram of a pole piece made of the metal-type negative electrode paste described in embodiment 14 of the present invention, applied to a ternary NCM523 system battery for 500 cycles.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The positive active material used by the positive pole piece in the embodiment of the invention is one or two or more of composite materials of lithium iron phosphate, lithium manganese phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium nickelate, lithium titanate, artificial graphite, natural modified graphite, soft carbon, hard carbon, carbon nano tube, graphene, composite graphite, mesophase carbon microsphere, expanded graphite material and the like.
The negative active material of the negative pole piece comprises a carbon negative active material and a high-capacity metal negative active material. The carbon negative active material is one or more of artificial graphite, natural modified graphite, soft carbon, hard carbon, composite graphite, mesocarbon microbeads, expanded graphite materials and the like; the high-capacity metal negative active material is one or more of aluminum, germanium, tin, antimony, zinc, germanium oxide, tin oxide, antimony oxide, zinc oxide, copper oxide and the like or a composite material. The inactive conductive foil current collector used for the negative electrode plate can be, but is not limited to, a non-porous copper foil, a non-porous nickel foil, a non-porous iron foil, a non-porous stainless steel foil, a porous copper foil, a porous nickel foil, a porous iron foil, a porous stainless steel foil, a copper mesh, a nickel mesh, an iron mesh, a stainless steel mesh, conductive carbon cloth and the like; the conductive agent in the negative pole piece is one or two or more of acetylene black, carbon black, Ketjen black, conductive graphite, carbon fiber, carbon nanowire, carbon nanotube, graphene and the like.
The secondary battery of the embodiment of the invention comprises a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode. The secondary battery may be prepared by various methods known to those skilled in the art, and for example, may include the steps of:
(1) preparing a positive plate: coating the positive electrode slurry on an aluminum foil positive electrode current collector to prepare a positive plate;
(2) preparing a negative plate: and (2) beating the binder into a glue solution according to a certain proportion, adding a high-capacity metal negative electrode active material, uniformly stirring and dispersing, then adding a conductive agent, uniformly stirring and dispersing to obtain uniform slurry, then adding a carbon negative electrode active material, uniformly stirring and dispersing, and coating the slurry on a non-active conductive foil current collector to prepare the negative electrode plate.
(3) Packaging: and sequentially laminating or winding the positive plate, the diaphragm and the negative plate to prepare a battery pole core, and packaging the battery pole core into a battery.
The packaging of the present invention includes placing the battery pole core into the battery case, welding the cover plate and the battery case, injecting the electrolyte into the battery case, forming and sealing the battery, and the forming, sealing and other techniques are various techniques known to those skilled in the art, and the present invention is not particularly limited. The present invention is not particularly limited to the positive electrode current collector, the positive electrode slurry, the electrolyte, and the separator of the present invention, and various positive electrode current collectors, positive electrode slurries, electrolytes, and separators known to those skilled in the art can be used.
Referring to fig. 1-2, fig. 1 is an SEM image of CNT coating on the surface of aluminum powder particles after CNT (carbon nanotube) and aluminum powder are added, stirred and dispersed in the process of preparing the metal-type negative electrode paste according to an embodiment of the present invention; fig. 2 is an SEM image of the metal-type negative electrode paste according to an embodiment of the present invention, in which CNTs (carbon nanotubes), aluminum powder, and graphite are added, and the mixture is stirred and dispersed.
As can be seen from the figure, the metal-type anode slurry provided by the embodiment of the present invention contains a high-capacity metal anode active material, a conductive agent, and a carbon-based anode active material; the conductive agent is well dispersed and coated on the surface of the high-capacity metal negative active material particles, the high-capacity metal negative active material particles and the conductive agent are uniformly dispersed among the carbon negative material particles, the slurry is coated on a negative pole piece made of a non-active conductive foil current collector, the high-capacity metal negative active material particles can be ensured to have good conductivity, and the high-capacity metal negative active material particles are filled in the middle of gaps formed by stacking the carbon material particles, so that the stacking density of the powder particles is improved. The stacking mode not only effectively utilizes the gaps existing when the carbon negative electrode large particles are stacked, but also ensures that the metal particles or the metal oxide particles dispersed in the gaps have certain deformation space when the volume changes during charging and discharging due to the gaps formed by stacking the carbon negative electrodes, reduces the damage of stress strain caused by the volume change, ensures that the high-capacity metal negative electrode active material particles are in good contact with the carbon negative electrode particles during the charging and discharging processes, and ensures that the conductivity of the whole pole piece is not changed. And the small-particle high-capacity metal negative active material can carry out lithium intercalation and lithium removal from the particle surface in an all-around manner and can intercalate lithium at a higher potential (more than 0.1V), so that the novel negative material and the secondary battery thereof have the performances of high energy density, high multiplying power, high safety, long cycle and the like.
The present invention will be described in further detail with reference to specific embodiments, which are described herein for the purpose of illustration only and are not to be construed as limiting the invention. The raw materials used in the examples and comparative examples were obtained commercially.
Example 1: secondary battery of negative pole piece prepared based on metal type negative pole slurry
The anode material adopts lithium iron phosphate (LFP), and the cathode pole piece is made of metal type cathode slurry. The high-capacity metal negative active material of the metal type negative electrode slurry is metal aluminum powder of D501.5um, the carbon negative active material is artificial graphite of D5015 um, and the current collector is 8um nonporous copper foil. Coating a lithium iron phosphate (LFP) positive electrode material with the specific capacity of 140mAh/g, PVDF and conductive carbon black on a double-sided aluminum foil according to the ratio of 95:3:2 to serve as a positive plate; preparing the artificial graphite cathode material with the full battery design specific capacity of 340mAh/g, the metal aluminum powder with the full battery design specific capacity of 750mAh/g, the conductive carbon black S-P and the binder PVDF into cathode slurry according to the proportion of 70:25:2: 3.
The preparation of the metal type negative electrode slurry comprises the steps of preparing PVDF glue solution according to a pulping process, adding metal aluminum powder for dispersion, adding a conductive agent for dispersion, and finally adding a pulping sequence of artificial graphite for dispersion to prepare uniform slurry to be coated on double-sided copper foil to serve as a negative electrode plate.
The processing technology and the process control of the positive and negative pole pieces adopt the current industrialized technology, and finally, the processed two cathodes and the positive pole are mixed with 1mol/L LiPF electrolyte6A mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of 1: 1), a diaphragm was a celgard2400 polypropylene porous membrane, and assembled into a full cell in a glove box filled with argon gas to obtain a battery sample C1.
To illustrate the beneficial effects of this example, we fabricated a battery core using a negative electrode made of a conventional negative electrode material and a pure metal aluminum powder negative electrode, and the specific fabrication process is as in comparative example 1 and comparative example 2.
Comparative example 1
The anode material adopts lithium iron phosphate (LFP), and the cathode pole piece is an artificial graphite material with D50 being 15 um. Coating a lithium iron phosphate anode material with the specific capacity of 140mAh/g with PVDF and conductive carbon black according to the ratio of 95:3:2Covering the double-sided aluminum foil as a positive plate; coating an artificial graphite negative electrode material with the specific capacity of 340mAh/g, a binder PVDF and conductive carbon black S-P on a double-sided copper foil according to the ratio of 95:3:2 to serve as a negative electrode sheet. The processing technology and the process control of the positive and negative pole pieces adopt the current industrialized technology, and finally, the processed negative pole and the positive pole are mixed with 1mol/L LiPF electrolyte6A mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1: 1), a diaphragm is a celgard2400 polypropylene porous membrane, and the whole cell is assembled in a glove box filled with argon gas to obtain a cell sample C00。
Comparative example 2
The anode material adopts lithium iron phosphate (LFP), and the cathode pole piece is metal aluminum powder with D50 being 1.5 um. Coating a lithium iron phosphate (LFP) positive electrode material with the specific capacity of 140mAh/g, PVDF and conductive carbon black on a double-sided aluminum foil according to the ratio of 95:3:2 to serve as a positive plate; and coating the metal aluminum powder negative electrode material with the specific capacity of 750mAh/g, a binder PVDF and conductive carbon black S-P on a double-sided copper foil according to a ratio of 95:3:2 to obtain the negative electrode sheet. The processing technology and the process control of the positive and negative pole pieces adopt the current industrialized technology, and finally, the processed negative pole and the positive pole are mixed with 1mol/L LiPF electrolyte6A mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1: 1), a diaphragm is a celgard2400 polypropylene porous membrane, and the whole cell is assembled in a glove box filled with argon gas to obtain a cell sample C01。
The battery core of the embodiment is subjected to charge and discharge tests under the condition that the voltage range is 2.3-3.65V by adopting the charge and discharge multiplying power of 0.2C, and the test results are shown in the following table 1.
TABLE 1 inventive example 1 and two comparative examples Battery test data
According to the test result, the secondary battery of the invention is intuitively displayed to effectively integrate two cathode active materials, and fully exert the advantages of the high-capacity metal cathode active material and the carbon cathode active material, thereby playing the roles of growing and shortening. When the metal aluminum powder is used as the anode material alone, the capacity of the metal aluminum powder is not exerted to half of the designed capacity, the cycle performance is very poor, and the capacity retention of 50 cycles is only 80.2% of the initial capacity. In contrast, the capacity of the secondary battery of the invention is kept to be 90.3 percent of the initial capacity after 500 cycles, and the energy density of the battery is as high as 625.2 Wh/L. The result shows that the secondary battery prepared from the negative pole piece prepared from the metal type negative pole slurry provided by the invention has the excellent effects of high capacity retention rate and high energy density.
Examples 2 to 13: taking metal aluminum powder as an example, the influence of different ratios of high-capacity metal negative active materials on the performance of the battery is researched
The difference between the examples 2 to 15 and the example 1 is that the content ratio of the metal aluminum powder in the negative electrode plate is 20 to 72 percent, the preparation steps of the positive electrode, the negative electrode plate, the electrolyte and the battery are the same, and the content ratio of the metal aluminum powder negative active material in the negative electrode plate is 20 to 72 percent.
The batteries of examples 2 to 13 were subjected to charge and discharge tests at a charge and discharge rate of 0.2C and a voltage range of 2.3 to 3.65V, and compared with example 1, the test results are shown in table 2 below:
TABLE 2 Battery test data for inventive examples 1-13
A cycle curve chart of the pole piece made of the metal-type negative electrode paste described in example 14 applied to the ternary NCM523 system battery for 500 cycles is shown in fig. 3.
Examples 16 to 29: taking metal aluminum powder as an example, the influence of different particle sizes of high-capacity metal negative active materials on the performance of the battery is researched
Examples 16 to 29 differ from example 1 in that the metal aluminum powder in the negative electrode sheet had different particle sizes, and the positive electrode, the negative electrode sheet, the electrolyte and the battery were prepared in the same manner, and the thickness of the metal aluminum powder negative active material in the negative electrode sheet was 25%.
The batteries of examples 16-29 were tested for charge and discharge at a charge and discharge rate of 0.2C and a voltage range of 2.3-3.65V, and compared to example 1, and the results are shown in Table 3 below:
TABLE 3 test data for batteries of inventive examples 1 and 14-25
Examples 30 to 47: influence of particle size difference of carbon-based negative electrode active material on battery performance (for example, artificial graphite)
Examples 30 to 47 are different from example 1 in that the artificial graphite material of the carbon-based negative active material in the negative electrode sheet has different particle sizes, and the steps of preparing the positive electrode, the negative electrode sheet, the electrolyte and the battery are the same, and the thickness of the artificial graphite negative active material in the negative electrode sheet accounts for 70%.
The batteries of examples 30 to 47 were subjected to charge and discharge tests at a charge and discharge rate of 0.2C and a voltage range of 2.3 to 3.65V, and compared with example 1, and the test results are shown in Table 4 below:
TABLE 4 test data for batteries of inventive examples 1 and 30-47
Examples 48 to 59: influence of kind-based carbon-based negative active material on battery performance
Examples 48 to 59 are different from example 1 in the kind of the carbon-based negative active material in the negative electrode sheet, and the steps of preparing the positive electrode, the negative electrode sheet, the electrolyte and the battery were the same. The batteries of examples 48 to 59 were subjected to the charge and discharge test at a charge and discharge rate of 0.2C and a voltage range of 2.3 to 3.65V, and compared with example 1, and the test results were as follows in Table 5:
TABLE 5 Battery test data for inventive examples 1 and 48-59
Examples 60 to 71: based on the influence of different types of conductive agents on the performance of the battery
Examples 60 to 71 differ from example 1 in the kind of conductive agent in the negative electrode sheet, and the steps of preparing the positive electrode, the negative electrode sheet, the electrolyte and the battery were the same. The batteries of examples 60 to 71 were subjected to charge and discharge tests at a charge and discharge rate of 0.2C and a voltage range of 2.3 to 3.65V, and compared with example 1, and the test results are shown in table 6 below:
TABLE 6 Battery test data for inventive examples 1 and 60-71
Examples 72 to 83: influence of using different current collectors on battery performance based on negative pole piece
Examples 72-83 differ from example 1 in the negative current collector in the negative electrode sheet, and the positive electrode, negative electrode sheet active material, electrolyte and cell preparation steps were the same. The batteries of examples 72 to 83 were subjected to charge and discharge tests at a charge and discharge rate of 0.2C and a voltage range of 2.3 to 3.65V, and compared with example 1, and the test results are shown in table 7 below:
TABLE 7 test data for batteries of examples 1 and 72-83 of the present invention
Examples 84 to 10: based on the influence of different kinds of positive active materials on the performance of the battery
Examples 84 to 104 are different from example 1 in the kind of the active material in the positive electrode sheet, and when the positive electrode active material in the positive electrode sheet contains a metal element, the method and the steps for producing the positive electrode sheet are the same as those in example 1. The preparation steps of the corresponding negative pole piece, electrolyte and battery are also the same as the embodiment 1; when the positive active material in the positive electrode sheet is a carbon material, the positive electrode sheet, the electrolyte preparation method, and the steps are the same as those in comparative example 3. The corresponding negative electrode tab and battery preparation steps were also the same as in comparative example 3.
Comparative example 3
The positive active material adopts mesocarbon microbeads, the negative pole piece is made of the metal type negative pole slurry, wherein the high-capacity metal negative active material is metal aluminum powder with the diameter of D501.5um, the carbon negative active material is artificial graphite with the diameter of D5015 um, and the current collector is 8um nonporous copper foil. The mesophase carbon microsphere positive electrode material with the specific capacity of 100mAh/g, PVDF and conductive carbon black are coated on a double-sided aluminum foil according to the ratio of 95:3:2 to be used as a positive electrode plate. The artificial graphite cathode material with the designed specific capacity of the full battery of 340mAh/g, the metal aluminum powder with the designed specific capacity of the full battery of 750mAh/g, the conductive carbon black S-P and the binder PVDF are prepared according to the proportion of 70:25:2:3, PVDF glue solution is firstly prepared according to the pulping process, then the metal aluminum powder is added for dispersion, then the conductive agent is added for dispersion, and finally, the uniform slurry is prepared by adding the artificial graphite in the pulping sequence and is coated on the double-sided copper foil to serve as a cathode pole piece. The processing technology and the process control of the positive and negative pole pieces adopt the current industrialized technology, and finally, the processed negative pole and the positive pole are mixed with 4mol/L LiPF electrolyte6The diaphragm is a celgard2400 polypropylene porous membrane, and the cell is assembled into a full cell in a glove box filled with argon to obtain a cell sample C03。
The batteries of examples 84-93 were tested for charge and discharge at a charge and discharge rate of 0.2C, in a voltage range of 2.5-4.2V for examples except that the charge and discharge voltage range of example 87 was 0.1-2.0V, and compared with example 1;
examples 94 to 104 and C03The battery is subjected to charge and discharge tests at a charge and discharge rate of 0.2C and under a voltage range of 3.0-4.6V. The test results are given in table 8 below:
TABLE 8 Battery test data for inventive examples 1 and 84-104 and comparative example C03
Examples 71 to 76: based on the influence of different diaphragm materials on the battery performance
Example 105-110 differs from example 1 in the type of separator material in the secondary battery, and the steps for preparing the positive electrode, the negative electrode, the electrolyte and the battery are the same. The electrochemical performance of the batteries of examples 71-76 was tested under the conditions of a test magnification of 0.2C and a voltage range of 2.3-3.65V. And compared to example 1, the test results are given in table 9 below:
TABLE 9 Battery test data for examples 1 and 105 and 110 of the present invention
Example 111-130: influence of negative pole piece based on different high-capacity metal negative active materials on battery performance
Example 111-130 differs from example 1 in the type of high-capacity metal negative active material in the negative electrode tab, and the steps of preparing the positive electrode, the negative electrode tab, the electrolyte and the battery are the same. The electrochemical performance of the battery obtained in example 111-130 was tested under the conditions of a test magnification of 0.2C and a voltage range of 2.3-3.65V. And compared to example 1, the test results are given in table 10 below:
TABLE 10 Battery test data for examples 1 and 111 and 130 of the present invention
Example 131-136: based on the influence of different conductive agent contents on the battery performance
The embodiment 131-136 is different from the embodiment 1 in the content of the conductive agent in the secondary battery, and the preparation steps of the positive electrode, the negative electrode plate, the electrolyte and the battery are the same. The electrochemical performance of the batteries of examples 71-76 was tested under the conditions of a test magnification of 0.2C and a voltage range of 2.3-3.65V. And compared to example 1, the test results are shown in table 11 below:
TABLE 11 Battery test data for examples 1 and 105 and 110 of the present invention
Example 137-142: based on the Effect of different Binder content on Battery Performance
Example 137-142 differs from example 1 in the binder content of the secondary battery, and the steps of preparing the positive electrode, the negative electrode plate, the electrolyte and the battery are the same. The electrochemical performance of the batteries of examples 71-76 was tested under the conditions of a test magnification of 0.2C and a voltage range of 2.3-3.65V. And compared to example 1, the test results are given in table 12 below:
TABLE 12 Battery test data for examples 1 and 105 and 110 of the present invention
In summary, compared with the research results of the article "research on modification of micron-sized spherical aluminum powder as negative electrode material of lithium ion battery" published by leixuefeng et al: when the aluminum powder with the grade of 3um is used as a negative electrode material, the capacity of the aluminum powder only plays 103mAh/g, the capacity of the aluminum powder is highest 592mAh after the aluminum powder is subjected to high-temperature carbon modification on the surface, the first efficiency is lower than 60%, and the capacity retention rate of the battery after the battery is circulated for 10 weeks is lower than 60%. And patent CN101937994.A "graphene/aluminum composite negative electrode material of lithium ion battery and preparation method thereof" proposes that the graphene/aluminum composite negative electrode material is prepared by adopting a way of ball milling of graphene and metal aluminum powder, the capacity of the material can reach 1100mAh/g, but the cycle is less than 10 weeks, and the capacity is kept lower than 80%. The gram capacity of the aluminum metal powder material in the metal negative electrode plate and the secondary battery prepared from the metal negative electrode slurry provided by the embodiment of the invention can be effectively exerted to be more than 700mAh, and the capacity retention rate of the secondary battery is more than 80% after the secondary battery is cycled for 500 weeks.
Compared with CN202010704786.0 composite material, its preparation method and negative electrode, the method proposes that high-capacity negative electrode material such as aluminum with high capacity is deposited on the surface of graphite particles, and then carbon is deposited or coated to make a negative electrode material with a three-layer structure, so as to improve the gram capacity and cycle performance of the negative electrode. The content proportion of the high-capacity metal negative active material in the metal type negative electrode slurry can reach higher (40%), and the negative electrode plate is simple in manufacturing process and low in cost.
Therefore, the metal type negative electrode slurry, the negative electrode plate and the secondary battery provided by the embodiment of the invention solve the problems that the capacity of a high-capacity metal material or a metal oxide material, particularly an aluminum micron material, cannot be exerted, the capacity is quickly attenuated in a circulating process and the like, and the secondary battery manufactured by adopting the negative electrode material has the performances of high safety, high energy density, long circulation and the like, and has the advantages of simple process and low manufacturing cost. Therefore, the metal type negative electrode slurry, the negative electrode plate and the secondary battery thereof have commercial prospect.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The metal type cathode slurry is characterized by comprising 55-95% of carbon cathode active materials and 1-40% of high-capacity metal cathode active materials in percentage by mass; the particle size of the carbon-based negative electrode active material is larger than that of the high-capacity metal negative electrode active material.
2. The metal-type anode slurry according to claim 1, wherein the carbon-based anode active material D50 is 4-20 um, and the high-capacity metal anode active material D50 is 0.5-10 um.
3. The metal-type anode slurry according to claim 1, wherein the high-capacity metal anode active material is one or more selected from aluminum, germanium, tin, antimony, zinc, germanium oxide, tin oxide, antimony oxide, zinc oxide, and copper oxide.
4. The metal-type anode slurry according to claim 1, wherein the carbon-based anode active material is selected from one or more of artificial graphite, natural modified graphite, soft carbon, hard carbon, composite graphite, mesocarbon microbeads and expanded graphite materials.
5. The metal-type anode slurry according to claim 1, further comprising 0-5% by mass of a conductive agent and 0.5-5% by mass of a binder.
6. The metal type negative electrode paste according to claim 5, wherein the conductive agent is one or more selected from acetylene black, carbon black, Ketjen black, conductive graphite, carbon fiber, carbon nanowire, carbon nanotube, and graphene.
7. The metal-type anode paste according to claim 5, wherein the binder is selected from PVDF and/or modified PVDF.
8. The method for preparing the metal-type anode slurry according to claim 5, wherein the metal-type anode slurry is obtained by stirring a binder into a glue solution, gradually adding a high-capacity metal anode active material, a conductive agent and a carbon anode active material, and uniformly dispersing.
9. A metal type negative pole piece is characterized in that the metal type negative pole slurry obtained in the claim 8 is uniformly coated on a negative pole current collector and is dried to obtain the metal type negative pole piece.
10. A secondary battery comprising the metal-type negative electrode sheet according to claim 9.
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| CN113972372A (en) * | 2021-09-26 | 2022-01-25 | 西安交通大学 | Metal graphite medium-temperature energy storage battery and preparation method thereof |
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