CN102709592B - Lithium ion secondary battery and preparation method thereof - Google Patents
Lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN102709592B CN102709592B CN201210178266.6A CN201210178266A CN102709592B CN 102709592 B CN102709592 B CN 102709592B CN 201210178266 A CN201210178266 A CN 201210178266A CN 102709592 B CN102709592 B CN 102709592B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 141
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 89
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 87
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 230000002427 irreversible effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 73
- 239000011248 coating agent Substances 0.000 claims description 61
- 238000000576 coating method Methods 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 33
- 239000007773 negative electrode material Substances 0.000 claims description 29
- 239000012530 fluid Substances 0.000 claims description 28
- 238000002347 injection Methods 0.000 claims description 28
- 239000007924 injection Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 238000004513 sizing Methods 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 26
- 239000006258 conductive agent Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002985 plastic film Substances 0.000 claims description 18
- 229920006255 plastic film Polymers 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007767 bonding agent Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- 238000011160 research Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000036961 partial effect Effects 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 238000007600 charging Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 212
- 230000009977 dual effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 14
- 239000003610 charcoal Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 240000006394 Sorghum bicolor Species 0.000 description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- ORJLWVJIEZZMSJ-UHFFFAOYSA-N N=[S+]F.[Li] Chemical compound N=[S+]F.[Li] ORJLWVJIEZZMSJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium ion secondary battery and a preparation method thereof, and belongs to the field of lithium ion secondary batteries. The anode layer of the lithium ion secondary battery has a layered structure, and comprises an anode current collector. An anode material layer consisting of two outer hard carbon material layers and a lithium metal layer between the two hard carbon material layers is adhered to one or two surfaces of the anode current collector, wherein the lithium metal layer is plated on the hard carbon material layers by adopting an ion sputtering method. An irreversible capacity compensation layer of the lithium ion secondary battery is the lithium metal layer sandwiched between the hard carbon material layers, is uniformly distributed, and can avoid the risk that a diaphragm is pierced by lithium metal or lithium dendrites, wherein the lithium ion secondary battery has the advantages of high charging and discharging efficiency, high safety and the like.
Description
Technical field
The present invention relates to a kind of battery and preparation method thereof, more particularly, the present invention relates to a kind of lithium rechargeable battery and preparation method thereof, belong to field of lithium ion secondary.
Background technology
Along with extensive use and the fast development of various portable electric appts and electric automobile, the demand to chemical power source and performance requirement sharp increase.Compare with other chemical power source, lithium ion battery is with advantage successes such as its long-life and high power characteristic and be widely used in fast mobile terminal electronic device field.At present, in commercialization lithium battery, mostly adopt lithium transition-metal oxide/graphite system.Along with developing rapidly of information technology, the portable set taking mobile phone, notebook computer as representative is constantly to miniaturization, slimming future development, and therefore the energy density to battery, cost and fail safe propose higher requirement.The performance of commercialization lithium battery more and more can not meet the requirement of above-mentioned development, and wherein negative material is one of important restraining factors.
Hard carbon cathode material has caused people's very big interest with higher capacity, low cost and the excellent cycle performance that its random sequence was had.Sony company obtains by thermal depolymerization furfuryl alcohol the Carbon Materials that specific capacity is 450mAh/g; Kanebo company reaches 580mAh/g with the reversible capacity that polyphenyl phenol is made the pyrolytic carbon negative material of presoma, far beyond the theoretical embedding lithium capacity 372mAh/g of graphite carbon material, thereby makes people carry out a large amount of research and development to it.In order to improve the volume energy density of hard carbon material, Ou Jung Kwon etc. has made hard charcoal ball taking phenolic resins as raw material, and it has higher compacted density (0.9g/mL) and less specific area (with respect to irregular hard charcoal class material).The employing hydrothermal methods such as Wang have been prepared a kind of nanostructured microsphere carbon cathode material, it is that outward appearance diameter is the charcoal ball of 5～10 μ m, in ball, be that the aperture of single graphite linings composition is at nano-pore or the pipe of 0.5～3.0 nm, it combines the height storage lithium ability of carbon nano-tube material and the excellent processing characteristics of spherical material with carbon element, energy density is higher by 30% than the MCMB material using at present, reach 400 mAh/g, be particularly useful for the needs of the large current work of lithium-ion-power cell, and cost is well below carbon nano-tube.Fail safe aspect, it is raw material that Osaka coal gasification company is used coal tar pitch, makes hard carbon material through 1100 DEG C of charings, and by analysis, this hard carbon material is crossed and while putting 120%, lithium metal just can be occurred and separate out, and by comparison, graphite cathode is crossed while putting 105% has lithium to separate out.Therefore, consider from the security performance of battery, hard carbon material is better than graphite.But, due to the design feature of hard charcoal itself, also there is many defects: as reversible lithium storage capacity with circulate to carry out attenuation ratio very fast; Also there is in addition the phenomenon (discharge potential is apparently higher than the charged electric potential of corresponding embedding lithium state) of voltage delay; But the most important thing is first charge-discharge irreversible capacity large (being generally greater than 20%), therefore seriously restricted the practical process of hard carbon material, fail so far commercial applications.
In order to reduce hard carbon material irreversible capacity first, improve the first charge-discharge efficiency of electrode, conventional method is to compensate the irreversible capacity first of hard carbon material with lithium powder/paper tinsel and lithiumation thing at present, and obtained certain effect as:
It is 200610089725.8 that State Intellectual Property Office discloses an application number in 2007.1.3, name is called the patent of invention of " preparation method of the hard charcoal-lithium metal composite negative pole material of lithium ion battery ", this patent is that hard carbon material is mixed under inert gas atmosphere with lithium powder, obtains hard charcoal-lithium metal composite negative pole material.Another kind method is: hard carbon material powder preparation is become to electrode slice; Then under inert gas atmosphere, lithium paper tinsel is compressed on to hard carbon resistance rod sheet surface, obtains hard charcoal-lithium metal composite negative pole material.In two kinds of methods, the mass ratio relation of lithium and hard carbon material meets: the superfluous discharge capacity first of lithium can compensate the irreversible capacity first of hard charcoal.The advantages such as the method negative material that can prepare that the present invention proposes has first coulomb more than 100%, electro-chemical activity is high, reversible capacity is large, good cycle, the cost of material is low, technological process is simple.
It is 201110093537.3 that State Intellectual Property Office discloses an application number in 2011.9.28, name is called the patent of invention of " a kind of high-capacity metal lithium powder composite cathode and preparation method and multi-layer composite electrode ", this patent discloses a kind of high-capacity metal lithium powder composite cathode of a kind of high-capacity metal lithium powder composite cathode and preparation method and multi-layer composite electrode, and composite negative pole weight portion consists of: 1～80 part of metallic lithium powder; 10～90 parts, negative pole powder; 1～10 part of conductive agent; 1～4.5 part of binding agent; 0～0.5 part, surfactant; The present invention improves specific discharge capacity and the volume and capacity ratio of negative material by Material claddings such as lithium metal powder and graphite, soft carbon, hard charcoal, tin and oxide, silicon and oxides thereof, reduce amount of active mass and improve battery specific capacity; Can regulate the specific capacity of negative pole by adjusting the ratio of lithium metal and graphite; Can effectively prevent that by the obstruct of insulating protective layer metallic dendrite growth from piercing through barrier film and causing battery internal short-circuit, improve the security performance of battery; Lithium metal powder is offset negative pole at irreversible capacity loss, has improved coulomb efficiency first of the negative materials such as graphite, hard charcoal, soft carbon, tin, silicon.
But there is certain defect in said method: first, lithium metal powder has higher activity, in the process of mixing with hard carbon material ball milling, very easily reunite, lithium powder pockety will cause the inconsistent of electrode charge and discharge state, and then causes battery capacity decay too fast; Secondly, lithium paper tinsel covers electrode surface, not only realization of industrialization process difficulty, and exist lithium paper tinsel to pierce through the risk of barrier film, reduce the fail safe of battery.
Summary of the invention
The present invention is intended to solve the lithium battery low defect of irreversible capacity first that contains hard carbon material, provides that a kind of fail safe is good, efficiency for charge-discharge high and low temperature excellent performance and suitable lithium ion battery filling soon and preparation method thereof.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of lithium rechargeable battery, comprise battery case, aluminum plastic film packaging bag, pole piece, positive pole ear, negative lug, described pole piece is followed successively by negative electrode layer, membrane layer, anodal layer and membrane layer from inside to outside, it is characterized in that: described negative electrode layer is layer structure, comprise negative current collector, the one side of described negative current collector or two sides are bonded with the negative electrode material layer being made up of hard carbon material layer and lithium metal level, and described negative electrode material layer is the lithium metal level between outside two-layer hard carbon material layer and two-layer hard carbon material layer.
Lithium metal level capacitance of the present invention equates with the total electric irreversible capacity of two-layer hard carbon material layer.
Hard carbon material layer of the present invention is to be formed by hard carbon material, conductive agent, binding agent and solvent.
Hard carbon material of the present invention is preferably starch base RESEARCH OF PYROCARBON and is made up of common process.
The proportioning of above-mentioned hard carbon material, conductive agent, binding agent and solvent is: hard carbon material 30～50%, conductive agent 0.5～3%, binding agent 0.5～3%, solvent 44～69%.
Above-mentioned hard carbon material is that resin carbon, organic polymer RESEARCH OF PYROCARBON or starch base RESEARCH OF PYROCARBON are made up of common process.
Above-mentioned resin carbon is phenolic resins, epoxy resin or poly furfuryl alcohol PFA-C; Organic polymer RESEARCH OF PYROCARBON is PFA, PVC, PVDF or PAN; Starch base RESEARCH OF PYROCARBON is rice starch, cornstarch, sorghum starch, wheaten starch tapioca, sweet potato starch or farina.
Anodal layer of the present invention is the positive pole of this area routine, comprises plus plate current-collecting body, loads on the positive electrode material layer on plus plate current-collecting body.
Above-mentioned positive electrode material layer is for to be formed by positive electrode, conductive agent, binding agent and solvent.
Positive electrode of the present invention is preferably cobalt acid lithium (LiCoO
2).
The proportioning of above-mentioned positive electrode, conductive agent, binding agent and solvent is: hard carbon material 40～60%, conductive agent 0.5～5%, binding agent 0.5～5%, solvent 25～59%.
The lithium ion battery various positive electrodes used that above-mentioned positive electrode is known to the skilled person, comprise cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMn
2o
4), lithium nickelate (LiNiO
2), LiFePO 4 (LiFePO
4), phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) or ternary material (LiCo
xni
ymn
1-x-yo
2).
Above-mentioned conductive agent is all conductive agents known in the field, comprises carbon fiber, graphite or carbon granule.
Above-mentioned binding agent is all binding agents known in the field, comprises Kynoar, SBR or polyvinyl alcohol.
Barrier film of the present invention is selected from the various membrane layers that well known to a person skilled in the art that lithium ion battery is used, comprises polypropylene micro-porous film (PP), microporous polyethylene film (PE), glass mat or PP/PE/PP, is preferably PP/PE/PP.
A preparation method for lithium rechargeable battery, is characterized in that: comprise following processing step:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 100～250 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 50～100 microns;
E, plating lithium metal level
Be 0.5 × 10 in vacuum degree
-2～2 × 10
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 10～50mA, and frequency is 50Hz, and the time is 2～10 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 0.5～3 micron;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 50～100 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
Adopt method known in those skilled in the art, the pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Adopt method known in those skilled in the art, inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Adopt method known in those skilled in the art, the battery core after fluid injection is once changed into processing;
K, partial volume
The method that adopts those skilled in the art to know altogether tests out the capacity of battery, obtains final lithium rechargeable battery product.
Coating thickness described in step B of the present invention is 150～200 microns.
Coating thickness described in step D of the present invention is 70～90 microns.
Injecting the electrolyte in step H gained battery core and leaving standstill described in step I of the present invention refers to and is first evacuated to vacuum degree >=-85kPa, and then fluid injection under 0.1～0.3MPa finally leaves standstill 3～15min and completes fluid injection.
Once changing into described in step J of the present invention processed and referred to that battery core is charged to 70%SOC state by the electric current of employing 0.05C.
The capacity that tests out battery described in step K of the present invention is specially:
A, constant-current discharge electric current: 0.5C, cut-ff voltage: 2.5V;
Shelve the time: 10min;
B, constant-current constant-voltage charging electric current: 0.5C, upper voltage limit: 3.8V, cut-off current: 0.05C;
Shelve: the time: 10min;
C, constant-current discharge: electric current: 0.5C, cut-ff voltage: 2.5V;
Shelve the time: 10min;
D, constant current charge: electric current: 0.5C, upper voltage limit: 3.3V.
Inert atmosphere of the present invention is any inert gas that this area is known altogether, is preferably argon gas or nitrogen.
Electrolyte of the present invention is for containing lithium salts and nonaqueous solvents, and described lithium salts can be one or more in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl Sulfonic Lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and lithium iodide; Described nonaqueous solvents can be gamma-butyrolacton, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, acid anhydrides, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, one or more in the ring-type organic ester of sulfur-bearing or unsaturated bond; The concentration of described lithium salts in electrolyte can be 0.3～4 mol/L, is preferably 0.5～2 mol/L.
Beneficial effect of the present invention is as follows:
1, the irreversible capacity layer of compensation of lithium ion secondary battery negative pole of the present invention is the lithium layer being clipped between hard carbon activity material layer, not only be evenly distributed but also can avoid lithium metal or Li dendrite to pierce through the risk of barrier film, therefore lithium ion battery of the present invention has the advantages such as efficiency for charge-discharge is high, fail safe is good.
2, to prepare the method preparation process of lithium rechargeable battery simple in the present invention, is suitable for suitability for industrialized production.The method adopts the method for ion sputtering, adopts technological parameter of the present invention, and the lithium layer of preparation has densification, uniform advantage;
3, in preparation method of the present invention, preferred positive electrode layer thickness and hard carbon material layer thickness are avoided because thickness is too thin, and the defects such as line, folding line and dew paper tinsel easily appear in coating procedure; In addition, avoid because thickness is too thick dry difficulty, the defect such as crackle, chip of easily makeing mistakes.Make it to reach a best thickness and send out scope.
4, barrier film of the present invention is selected PP/PE/PP, utilizes the closed pore effect of intermediate layer PE, improves the barrier of barrier film, and then can promote the fail safe of battery;
5, hard carbon material of the present invention is selected starch base RESEARCH OF PYROCARBON, it is with low cost, specific capacity is high, good cycle, low temperature and high rate performance good.
Brief description of the drawings
Fig. 1 is the structural representation of lithium rechargeable battery of the present invention;
Fig. 2 is the layer structure schematic diagram of negative electrode layer in lithium rechargeable battery of the present invention.
Reference numeral: 110 be battery case, 120 for aluminum plastic film packaging bag, 130 for pole piece, 140 for positive pole ear, 150 for negative lug, 131 for negative electrode layer, 132 for membrane layer, 133 for anodal layer, 210 for negative current collector, 220 for negative electrode material layer, 221 for hard carbon material layer, 222 be lithium metal level.
Embodiment
embodiment 1
A kind of lithium rechargeable battery, comprise battery case, aluminum plastic film packaging bag, pole piece, positive pole ear, negative lug, described pole piece is followed successively by negative electrode layer, membrane layer, anodal layer and membrane layer from inside to outside, described negative electrode layer is layer structure, comprise negative current collector, the one side of described negative current collector or two sides are bonded with the negative electrode material layer being made up of hard carbon material layer and lithium metal level, and described negative electrode material layer is the lithium metal level between outside two-layer hard carbon material layer and two-layer hard carbon material layer.
embodiment 2
On the basis of embodiment 1, be preferably:
Described lithium metal level capacitance equates with the total electric irreversible capacity of two-layer hard carbon material layer.
Described hard carbon material layer is to be formed by hard carbon material, conductive agent, binding agent and solvent.
Described hard carbon material is that starch base RESEARCH OF PYROCARBON is made up of common process.
Described membrane layer is PP/PE/PP.
embodiment 3
The preparation method of lithium rechargeable battery of the present invention:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 100 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 50 microns;
E, plating lithium metal level
Be 0.5 × 10 in vacuum degree
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 10mA, and frequency is 50Hz, and the time is 2 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 0.5 micron;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 50 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
embodiment 4
The preparation method of lithium rechargeable battery of the present invention:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 250 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 100 microns;
E, plating lithium metal level
Be 2 × 10 in vacuum degree
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 50mA, and frequency is 50Hz, and the time is 10 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 3 microns;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 100 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
embodiment 5
The preparation method of lithium rechargeable battery of the present invention:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 175 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 75 microns;
E, plating lithium metal level
Be 1.25 × 10 in vacuum degree
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 30mA, and frequency is 50Hz, and the time is 6 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 1.75 microns;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 75 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
embodiment 6
The preparation method of lithium rechargeable battery of the present invention:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 200 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 65 microns;
E, plating lithium metal level
Be 1.5 × 10 in vacuum degree
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 43mA, and frequency is 50Hz, and the time is 3.5 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 2 microns;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 65 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
embodiment 7
On the basis of embodiment 3～6, preferred:
It is 150 microns at the coating thickness described in step B.
It is 70 microns at the coating thickness described in step D.
Described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree-85kPa that then fluid injection under 0.1MPa finally leaves standstill 3min and completes fluid injection.
Described inert atmosphere argon gas or nitrogen.
embodiment 8
On the basis of embodiment 3～6, preferred:
It is 200 microns at the coating thickness described in step B.
It is 90 microns at the coating thickness described in step D.
Described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree-50kPa that then fluid injection under 0.3MPa finally leaves standstill 15min and completes fluid injection.
Described inert atmosphere argon gas or nitrogen.
embodiment 9
On the basis of embodiment 3～6, preferred:
It is 175 microns at the coating thickness described in step B.
It is 80 microns at the coating thickness described in step D.
Described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree-65kPa that then fluid injection under 0.2MPa finally leaves standstill 9min and completes fluid injection.
Described inert atmosphere argon gas or nitrogen.
embodiment 10
On the basis of embodiment 3～6, preferred:
It is 195 microns at the coating thickness described in step B.
It is 85 microns at the coating thickness described in step D.
Described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree-70kPa that then fluid injection under 0.15MPa finally leaves standstill 11min and completes fluid injection.
Described inert atmosphere argon gas or nitrogen.
embodiment 11
A kind of lithium rechargeable battery, comprise battery case, aluminum plastic film packaging bag, pole piece, positive pole ear, negative lug, described pole piece is followed successively by negative electrode layer, membrane layer, anodal layer and membrane layer from inside to outside, it is characterized in that: described negative electrode layer is layer structure, comprise negative current collector, the one side of described negative current collector or two sides are bonded with the negative electrode material layer being made up of hard carbon material layer and lithium metal level, and described negative electrode material layer is the lithium metal level between outside two-layer hard carbon material layer and two-layer hard carbon material layer.
Described lithium metal level capacitance equates with the total electric irreversible capacity of two-layer hard carbon material layer.
Described hard carbon material layer is to be formed by hard carbon material, conductive agent, binding agent and solvent.
Described hard carbon material is that starch base RESEARCH OF PYROCARBON is made up of common process.
Described membrane layer is PP/PE/PP.
A preparation method for lithium rechargeable battery, is characterized in that: comprise following processing step:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 100～250 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 50～100 microns;
E, plating lithium metal level
Be 0.5 × 10 in vacuum degree
-2～2 × 10
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 10～50mA, and frequency is 50Hz, and the time is 2～10 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D, and thickness is 0.5～3 micron;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 50～100 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
It is 150～200 microns at the coating thickness described in step B.
It is 70～90 microns at the coating thickness described in step D.
Described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree >=-85kPa that then fluid injection under 0.1～0.3MPa finally leaves standstill 3～15min and completes fluid injection.
Described inert atmosphere argon gas or nitrogen.
embodiment 12
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 200 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of rice starch pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 100 microns, dry; The energy density of gained negative pole is 0.6mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 100 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.6mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 13
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 200 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of cornstarch pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 50 microns, dry; The energy density of gained negative pole is 0.3mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 150 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.9mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 14
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 200 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of sorghum starch pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 150 microns, dry; The energy density of gained negative pole is 0.9mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 50 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.6mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 15
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 150 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of wheaten starch pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 100 microns, dry; The energy density of gained negative pole is 0.6mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 100 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.6mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 16
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 150 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of sweet potato starch pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 100 microns, dry; The energy density of gained negative pole is 0.6mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 100 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.6mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 17
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, prepare anode sizing agent according to the method that those skilled in the art are in common knowledge; By slurry dual coating on the aluminium foil of 16 microns, thickness is 150 microns; Be dried, roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopting the prepared hard charcoal of farina pyrolysis is negative electrode active material, prepares cathode size according to the method that those skilled in the art are in common knowledge; By cathode size dual coating on the Copper Foil of 12 microns, thickness is 100 microns, dry; The energy density of gained negative pole is 0.6mAh/cm
2.
Li layer: at above-mentioned negative terminal surface deposition layer of metal Li, energy density is 0.2mAh/cm
2.
Negative pole: by the above-mentioned cathode size surperficial dual coating that contains Li, thickness is 100 microns, is dried, rolls, cuts into slices; The energy density of gained negative pole is 0.6mAh/cm
2.
Pole piece: the positive pole of preparing with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, reels and makes in humidity-controlled environment with negative pole/barrier film/positive pole.
Lithium battery: prepare pole piece with said method and be encapsulated in aluminum plastic film, and inject a small amount of electrolyte.The preparation method of lithium battery can be those skilled in the art's method in common knowledge.
Contrast preparation:
Adopt said method to prepare negative pole and lithium battery, difference is in the middle of negative pole, there is no Li layer.
embodiment 18
Electrochemical property test
The prepared battery design capacity of embodiment 12～17 and comparative example is 450mAh(0.5C electric discharge).Under room temperature, the lithium ion battery that embodiment 12～17 and contrast are made is with 0.2mAh/cm
2charging.Battery upper voltage limit 4.2V, with 0.5 mAh/cm
2electric discharge, lower voltage limit 3.0V.One time charge and discharge process is a circulation, records discharge capacity for the first time.After 50 circulations, measure the capacity of battery, and calculated capacity surplus ratio.As shown in table 1.
Table 1
Can find out from embodiment 12～18 and contrast preparation 12～18, the lithium ion battery that contains lithium layer first discharge capacity close to design capacity, and not containing the lithium ion battery of lithium layer first irreversible capacity be 20% left and right; The cyclicity that contains in addition the lithium ion battery of lithium layer is also obviously better than the not battery containing lithium layer.
Claims (9)
1. a lithium rechargeable battery, comprise battery case, aluminum plastic film packaging bag, pole piece, positive pole ear, negative lug, described pole piece is followed successively by negative electrode layer, membrane layer, anodal layer and membrane layer from inside to outside, it is characterized in that: described negative electrode layer is layer structure, comprise negative current collector, the one side of described negative current collector or two sides are bonded with the negative electrode material layer being made up of hard carbon material layer and lithium metal level, and described negative electrode material layer is the lithium metal level between outside two-layer hard carbon material layer and two-layer hard carbon material layer;
Described lithium rechargeable battery is made by following methods:
A, prepare anode sizing agent
Positive electrode, conductive agent, bonding agent and solvent are evenly mixed to get to anode sizing agent;
B, the anodal layer of preparation
Anode sizing agent prepared steps A is evenly coated in to one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, coating thickness is 100～250 microns, and positive electrode material layer and plus plate current-collecting body form anodal layer;
C, prepare cathode size
Hard carbon material, conductive agent, bonding agent and solvent are evenly mixed to get to cathode size;
D, coating cathode size
Cathode size prepared step C is evenly coated in to one side or the two sides of negative current collector, forms hard carbon material layer, coating thickness is 50～100 microns;
E, plating lithium metal level
Be 0.5 × 10 in vacuum degree
-2～2 × 10
-2in the vacuum environment of mbar, adopt the method for ion sputtering, control sputtering current is 10～50mA, and frequency is 50Hz, and the time is 2～10 minutes, and lithium is evenly plated in to the hard carbon material layer surface in step D;
F, prepare negative electrode layer
In inert atmosphere, cathode size prepared step C is evenly coated in to the lithium layer on surface of metal in step e, form hard carbon material layer, coating thickness is 50～100 microns, two-layer hard carbon material layer and the lithium metal level between them form negative electrode material layer, and negative electrode material layer and negative current collector form negative electrode layer;
G, prepare pole piece
According to the order that is followed successively by from inside to outside negative electrode layer, membrane layer, anodal layer and membrane layer, adopt common process to reel in anodal layer, negative electrode layer and barrier film, make pole piece;
H, heat-sealing
The pole piece that step G is made is put into aluminum plastic film packaging bag heat-sealing, makes battery core;
I, fluid injection
Inject the electrolyte in step H gained battery core and leave standstill;
J, once change into
Battery core after fluid injection is once changed into processing;
K, partial volume
Test out the capacity of battery, obtain final lithium rechargeable battery product.
2. a kind of lithium rechargeable battery according to claim 1, is characterized in that: described lithium metal level capacitance equates with the total electric irreversible capacity of two-layer hard carbon material layer.
3. a kind of lithium rechargeable battery according to claim 1, is characterized in that: described hard carbon material layer is to be formed by hard carbon material, conductive agent, binding agent and solvent.
4. according to a kind of lithium rechargeable battery described in claim 1 or 3, it is characterized in that: described hard carbon material is that starch base RESEARCH OF PYROCARBON is made up of common process.
5. a kind of lithium rechargeable battery according to claim 1, is characterized in that: described membrane layer is PP/PE/PP.
6. a kind of lithium rechargeable battery according to claim 1, is characterized in that: be 150～200 microns at the coating thickness described in step B.
7. a kind of lithium rechargeable battery according to claim 1, is characterized in that: be 70～90 microns at the coating thickness described in step D.
8. a kind of lithium rechargeable battery according to claim 1, it is characterized in that: described in step I inject the electrolyte into step H gained battery core in and leave standstill and refer to and be first evacuated to vacuum degree >=-85kPa, then fluid injection under 0.1～0.3MPa, finally leaves standstill 3～15min and completes fluid injection.
9. a kind of lithium rechargeable battery according to claim 1, is characterized in that: described inert atmosphere is argon gas or nitrogen.
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| JPWO2014156092A1 (en) * | 2013-03-29 | 2017-02-16 | 三洋電機株式会社 | Lithium ion battery |
| CN105470450A (en) * | 2014-10-16 | 2016-04-06 | 万向A一二三系统有限公司 | Silicon negative electrode plate for lithium-ion power battery and preparation method of silicon negative electrode plate |
| CN105591071B (en) * | 2014-10-24 | 2018-01-12 | 宁德时代新能源科技股份有限公司 | Lithium metal anode sheet, preparation method thereof and lithium metal battery |
| KR102484893B1 (en) * | 2017-10-26 | 2023-01-04 | 현대자동차주식회사 | A cathode of a lithium metal secondary battery and a lithium metal secondary battery including the same |
| KR102439128B1 (en) * | 2018-07-06 | 2022-09-02 | 주식회사 엘지에너지솔루션 | Negative electrode for lithium secondary battery, prelithiation method thereof, and lithium secondary battery comprising the same |
| CN112825354B (en) * | 2019-11-20 | 2023-03-21 | 郑州宇通集团有限公司 | Lithium negative electrode, preparation method thereof and lithium secondary battery |
| CN113540398A (en) * | 2020-04-17 | 2021-10-22 | 北京卫国创芯科技有限公司 | High-energy-density lithium battery cathode and preparation method thereof |
| CN111653727B (en) * | 2020-06-30 | 2022-05-17 | 陕西煤业化工技术研究院有限责任公司 | Pre-lithiation silicon-based thin film negative electrode material and preparation method thereof |
| CN111900373B (en) * | 2020-08-04 | 2021-08-06 | 大连理工大学 | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material |
| CN111967190B (en) * | 2020-08-24 | 2023-01-31 | 哈尔滨理工大学 | Lithium battery safety degree evaluation method and device based on lithium dendrite morphology image recognition |
| EP4329014A1 (en) * | 2022-06-09 | 2024-02-28 | Contemporary Amperex Technology Co., Limited | Secondary battery, battery module comprising secondary battery, battery pack, and electric device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1581538A (en) * | 2004-05-21 | 2005-02-16 | 惠州Tcl金能电池有限公司 | Method for manufacturing secondary metal lighium cell cathode |
| CN1889288A (en) * | 2006-07-14 | 2007-01-03 | 清华大学 | Method for producing hard carbon lithium metal composite negative pole material for lithium ion battery |
| CN101728513A (en) * | 2009-12-03 | 2010-06-09 | 武汉大学 | Compound for anode material of lithium ion secondary battery and preparation method thereof |
| CN101783401A (en) * | 2009-01-15 | 2010-07-21 | 比亚迪股份有限公司 | Cathode and Li-ion battery comprising same |
| CN202633454U (en) * | 2012-06-01 | 2012-12-26 | 中国东方电气集团有限公司 | Lithium ion secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4517560B2 (en) * | 2001-12-28 | 2010-08-04 | 日本電気株式会社 | Lithium ion secondary battery and method of using lithium secondary battery |
-
2012
- 2012-06-01 CN CN201210178266.6A patent/CN102709592B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1581538A (en) * | 2004-05-21 | 2005-02-16 | 惠州Tcl金能电池有限公司 | Method for manufacturing secondary metal lighium cell cathode |
| CN1889288A (en) * | 2006-07-14 | 2007-01-03 | 清华大学 | Method for producing hard carbon lithium metal composite negative pole material for lithium ion battery |
| CN101783401A (en) * | 2009-01-15 | 2010-07-21 | 比亚迪股份有限公司 | Cathode and Li-ion battery comprising same |
| CN101728513A (en) * | 2009-12-03 | 2010-06-09 | 武汉大学 | Compound for anode material of lithium ion secondary battery and preparation method thereof |
| CN202633454U (en) * | 2012-06-01 | 2012-12-26 | 中国东方电气集团有限公司 | Lithium ion secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-203625A 2003.07.18 |
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