CN202616342U - Lithium-ion secondary battery negative pole - Google Patents
Lithium-ion secondary battery negative pole Download PDFInfo
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- CN202616342U CN202616342U CN2012202561172U CN201220256117U CN202616342U CN 202616342 U CN202616342 U CN 202616342U CN 2012202561172 U CN2012202561172 U CN 2012202561172U CN 201220256117 U CN201220256117 U CN 201220256117U CN 202616342 U CN202616342 U CN 202616342U
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 101
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 76
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- 229920002472 Starch Polymers 0.000 claims description 20
- 239000008107 starch Substances 0.000 claims description 20
- 235000019698 starch Nutrition 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 239000002296 pyrolytic carbon Substances 0.000 claims description 17
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- 238000000576 coating method Methods 0.000 claims description 12
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- 239000011347 resin Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 abstract description 97
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 34
- 230000002427 irreversible effect Effects 0.000 abstract description 9
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract 5
- 239000011229 interlayer Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 239000006258 conductive agent Substances 0.000 description 14
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- 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
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 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
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- 240000006394 Sorghum bicolor Species 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
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- 239000010406 cathode material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
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- 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
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 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
- 235000012419 Thalia geniculata Nutrition 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
- 239000011149 active material Substances 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000013461 design 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 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
- BMANCNNUKXPJTN-UHFFFAOYSA-N lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BMANCNNUKXPJTN-UHFFFAOYSA-N 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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 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
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- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical class [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The utility model discloses a lithium-ion secondary battery negative pole and belongs to the technical field of lithium-ion secondary batteries. The lithium-ion secondary battery negative pole is of layer structure, one side or two sides of a negative current collector is bonded with a negative material layer which is composed of hard carbon material layers and lithium metal layers, and the negative material layer is two hard carbon material layers on an outer side and the lithium metal layers between the two hard carbon material layers. Due to the facts that two sides of the current collector are both loaded with hard carbon material layers of interlayer structure, an irreversible capacity compensation layer is a lithium layer arranged between the hard carbon material layers, and the structure is even in distribution and can avoid the risk that lithium metal or lithium dendrites pierce a separating film. Thus, lithium batteries manufactured by the lithium-ion secondary battery negative pole has the advantages of being high in charge-discharge efficiency and good in safety.
Description
Technical field
The utility model relates to a kind of electrode of battery, and more particularly, the utility model relates to a kind of lithium ion secondary battery negative pole, belongs to technical field of lithium ion secondary.
Background technology
Along with the extensive use and the fast development of various portable electric appts and electric automobile, to the demand and the performance requirement sharp increase of chemical power source.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 mobile electronic device field, terminal.At present, adopt lithium transition-metal oxide/graphite system in the commercialization lithium battery mostly.Along with developing rapidly of information technology, be that the portable set of representative constantly develops to miniaturization, slimming direction with mobile phone, notebook computer, therefore energy density, cost and the fail safe to battery proposes higher requirement.The performance of commercialization lithium battery more and more can not satisfy 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 ordering was had.Sony company obtains the raw material of wood-charcoal material that specific capacity is 450mAh/g through the thermal depolymerization furfuryl alcohol; The reversible capacity that Kanebo company makes the pyrolytic carbon negative material of presoma with polyphenyl phenol reaches 580mAh/g, the theoretical embedding lithium capacity 372mAh/g of graphite-like raw material of wood-charcoal material head and shoulders above, thus make people carry out a large amount of research and development to it.In order to improve the volume energy density of hard raw material of wood-charcoal material, Ou Jung Kwon etc. are that raw material has been processed hard charcoal ball with phenolic resins, and it has higher compacted density (0.9g/mL) and less specific area (with respect to irregular hard charcoal class material).Employing hydrothermal methods such as Wang have prepared a kind of nanostructured microsphere carbon cathode material; It is that the outward appearance diameter is the charcoal ball of 5～10 μ m; In the ball nano-pore or the pipe of the aperture of single graphite linings composition at 0.5～3.0 nm; It has combined the height storage lithium ability of carbon nano-tube material and the excellent processing characteristics of spherical material with carbon element, and energy density is higher by 30% than the MCMB material that is using at present, reaches 400 mAh/g; The needs that are particularly useful for the big current work of lithium-ion-power cell, and cost is well below CNT.The fail safe aspect, coal gasification company in Osaka uses coal tar pitch to be raw material, makes hard raw material of wood-charcoal material through 1100 ℃ of charings, and through analyzing, this hard raw material of wood-charcoal material is crossed to put and lithium metal just can take place in 120% o'clock separated out, and by comparison, graphite cathode is crossed to put promptly had lithium to separate out at 105% o'clock.Therefore, consider that hard raw material of wood-charcoal material is better than graphite from the security performance of battery.But, because also there are many defectives in the design feature of hard charcoal itself: as the reversible lithium storage capacity with circulate to carry out attenuation ratio very fast; The phenomenon (discharge potential is apparently higher than the charged electric potential of the embedding lithium state of correspondence) that also has voltage delay in addition; But the most important thing is first charge-discharge irreversible capacity big (generally greater than 20%), therefore seriously restricted the practicability process of hard raw material of wood-charcoal material, fail commercial applications so far.
In order to reduce hard raw material of wood-charcoal material irreversible capacity first, improve the first charge-discharge efficiency of electrode, method commonly used at present is to compensate the irreversible capacity first of hard raw material of wood-charcoal material with lithium powder/paper tinsel and lithiumation thing, 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 " lithium ion battery is with the preparation method of hard charcoal-lithium metal composite negative pole material "; This patent is that hard raw material of wood-charcoal material is mixed under inert gas atmosphere with the lithium powder, obtains hard charcoal-lithium metal composite negative pole material.Another kind method is: hard raw material of wood-charcoal material powder preparation is become electrode slice; Under inert gas atmosphere, the lithium paper tinsel is compressed on hard carbon resistance rod sheet surface then, obtains hard charcoal-lithium metal composite negative pole material.Lithium is satisfied with the mass ratio relation of hard raw material of wood-charcoal material in two kinds of methods: the superfluous first discharge capacity of lithium can compensate the irreversible capacity first of hard charcoal.The negative material that the method that the present invention proposes can prepare has first coulomb more than 100%, advantages such as electro-chemical activity is high, reversible capacity is big, 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 power capacity metallic lithium powder composite negative pole and preparation method and MULTILAYER COMPOSITE electrode "; This patent discloses a kind of high power capacity metallic lithium powder composite negative pole and preparation method and a kind of high power capacity metallic lithium powder of MULTILAYER COMPOSITE electrode composite negative pole, and the composite negative pole weight portion consists of: 1～80 part of metallic lithium powder; 10～90 parts in negative pole powder; 1～10 part of conductive agent; 1～4.5 part of binding agent; 0～0.5 part in surfactant; The present invention reduces the active material consumption and improves the battery specific capacity through the specific discharge capacity and the volume and capacity ratio of lithium metal powder and graphite, soft carbon, hard charcoal, tin and the compound raising negative materials of material such as oxide, silicon and oxide thereof thereof; The specific capacity that can regulate negative pole through the ratio of adjustment lithium metal and graphite; Obstruct through insulating protective layer can prevent effectively that metallic dendrite growth diaphragm from causing the battery internal short-circuit, improves the security performance of battery; Lithium metal powder is offset negative pole at irreversible capacity loss, has improved the efficient of enclosed pasture first of negative materials such as graphite, hard charcoal, soft carbon, tin, silicon.
But there is certain defective in said method: at first, lithium metal powder has higher activity; Grinding in the process of mixing with hard raw material of wood-charcoal pellet; Very easily reunite, lithium powder pockety will cause the inconsistent of electrode charge and discharge attitude, and then causes the battery capacity decay too fast; Secondly, the lithium paper tinsel covers electrode surface, and not only the realization of industrialization process is difficult, and has the risk of lithium paper tinsel diaphragm, has reduced the fail safe of battery.
The utility model content
The utility model is intended to solve the lithium battery low defective of irreversible capacity first that contains hard raw material of wood-charcoal material, provides that a kind of fail safe is good, efficiency for charge-discharge high and low temperature excellent performance and the suitable lithium ion battery negative that fills soon.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of lithium ion secondary battery negative pole; Comprise negative current collector; It is characterized in that: described lithium ion secondary battery negative pole is a layer structure; Described negative current collector one side or two sides are bonded with the negative electrode material layer of being made up of the hard raw material of wood-charcoal bed of material and lithium metal level, and described negative electrode material layer is the two-layer hard raw material of wood-charcoal bed of material of outside and the lithium metal level between the two-layer hard raw material of wood-charcoal bed of material.
In the described negative electrode material layer of the utility model near the hard raw material of wood-charcoal bed of material and tight contact bonding of collector one side with negative current collector.
The described two-layer hard raw material of wood-charcoal bed of material of the utility model closely contacts with lithium metal level between the hard raw material of wood-charcoal bed of material.
The area of the contact-making surface between the described negative current collector of the utility model, lithium metal level and the hard raw material of wood-charcoal bed of material equates.
The described hard raw material of wood-charcoal bed of material of the utility model is meant that the hard raw material of wood-charcoal material and conductive agent, binding agent and the solvent that are formed by resin carbon, organic polymer RESEARCH OF PYROCARBON or starch base RESEARCH OF PYROCARBON form.
Above-mentioned hard raw material of wood-charcoal material is preferably the starch base RESEARCH OF PYROCARBON.
Above-mentioned conductive agent is all conductive agents known in the field, comprises carbon fiber, graphite, carbon granule.
Above-mentioned binding agent is all binding agents known in the field, comprises Kynoar, gathers butadiene-styrene rubber, polyvinyl alcohol.
Above-mentioned resin carbon-coating is phenolic resins layer, epoxy resin layer or poly furfuryl alcohol layer; Described organic polymer pyrolytic carbon layer is polytetrafluoroethylene floor (PFA), polyvinyl chloride layer (PVC), Kynoar (PVDF) layer or gathers second polyacrylonitrile layer (PAN); Described starch base RESEARCH OF PYROCARBON is rice starch layer, cornstarch layer, sorghum starch layer, wheaten starch layer, para arrowroot bisque, sweet potato starch layer or farina layer.
The thickness of the described negative current collector of the utility model is 8～20 microns.
The described lithium metal layer thickness of the utility model is 0.5～3 micron.
The thickness of the described hard raw material of wood-charcoal bed of material of the utility model is 50～100 microns.
The useful technique effect that the utility model brings:
Since the lithium ion battery negative of the utility model on the collector two sides all load the hard raw material of wood-charcoal bed of material of sandwich; The irreversible capacity layer of compensation is the lithium layer that is clipped between the hard raw material of wood-charcoal bed of material; Not only be evenly distributed but also this structure can be avoided the risk of lithium metal or Li dendrite diaphragm, therefore adopt the lithium ion battery of the negative pole preparation of the utility model structure to have efficiency for charge-discharge height, advantage that fail safe is good.
Description of drawings
Figure of description is the layer structure sketch map of the utility model lithium ion secondary battery negative pole.
Reference numeral: 10 is that negative current collector, 20 is that negative electrode material layer, 21 is that the hard raw material of wood-charcoal bed of material, 22 is the lithium metal level.
Embodiment
Embodiment 1
A kind of lithium ion secondary battery negative pole; Comprise negative current collector 10; Described lithium ion secondary battery negative pole is a layer structure; Described negative current collector 10 one sides or two sides are bonded with the negative electrode material layer of being made up of the hard raw material of wood-charcoal bed of material 21 and lithium metal level 22 20, and described negative electrode material layer 20 is the two-layer hard raw material of wood-charcoal bed of material 21 of outside and the lithium metal level 22 between the two-layer hard raw material of wood-charcoal bed of material 21.
Embodiment 2
According to embodiment 1, preferred:
In the described negative electrode material layer 20 near the hard raw material of wood-charcoal bed of material 21 and negative current collector 10 bonding and tight contacts of negative current collector 10 1 sides.
The described two-layer hard raw material of wood-charcoal bed of material 21 closely contacts with lithium metal level 22 between the two-layer hard raw material of wood-charcoal bed of material 21.
The area of the contact-making surface between described negative current collector 10, lithium metal level 22 and the hard raw material of wood-charcoal bed of material 21 equates.
The described hard raw material of wood-charcoal bed of material 21 is resin carbon-coating, organic polymer pyrolytic carbon layer or starch base pyrolytic carbon layer.
The described hard raw material of wood-charcoal bed of material 21 is the starch base pyrolytic carbon layer.
The thickness of described negative current collector 10 is 8 microns.
The thickness of described lithium metal level 22 is 0.5 micron.
The thickness of the described hard raw material of wood-charcoal bed of material 21 is 50 microns.
Embodiment 3
According to embodiment 1, preferred:
In the described negative electrode material layer 20 near the hard raw material of wood-charcoal bed of material 21 and negative current collector 10 bonding and tight contacts of negative current collector 10 1 sides.
The described two-layer hard raw material of wood-charcoal bed of material 21 closely contacts with lithium metal level 22 between the two-layer hard raw material of wood-charcoal bed of material 21.
The area of the contact-making surface between described negative current collector 10, lithium metal level 22 and the hard raw material of wood-charcoal bed of material 21 equates.
The described hard raw material of wood-charcoal bed of material 21 is resin carbon-coating, organic polymer pyrolytic carbon layer or starch base pyrolytic carbon layer.
The described hard raw material of wood-charcoal bed of material 21 is the starch base pyrolytic carbon layer.
The thickness of described negative current collector 10 is 20 microns.
The thickness of described lithium metal level 22 is 3 microns.
The thickness of the described hard raw material of wood-charcoal bed of material 21 is 100 microns.
Embodiment 4
According to embodiment 1, preferred:
In the described negative electrode material layer 20 near the hard raw material of wood-charcoal bed of material 21 and negative current collector 10 bonding and tight contacts of negative current collector 10 1 sides.
The described two-layer hard raw material of wood-charcoal bed of material 21 closely contacts with lithium metal level 22 between the two-layer hard raw material of wood-charcoal bed of material 21.
The area of the contact-making surface between described negative current collector 10, lithium metal level 22 and the hard raw material of wood-charcoal bed of material 21 equates.
The described hard raw material of wood-charcoal bed of material 21 is resin carbon-coating, organic polymer pyrolytic carbon layer or starch base pyrolytic carbon layer.
The described hard raw material of wood-charcoal bed of material 21 is the starch base pyrolytic carbon layer.
The thickness of described negative current collector 10 is 14 microns.
The thickness of described lithium metal level 22 is 1.75 microns.
The thickness of the described hard raw material of wood-charcoal bed of material 21 is 75 microns.
Embodiment 5
According to embodiment 1, preferred:
In the described negative electrode material layer 20 near the hard raw material of wood-charcoal bed of material 21 and negative current collector 10 bonding and tight contacts of negative current collector 10 1 sides.
The described two-layer hard raw material of wood-charcoal bed of material 21 closely contacts with lithium metal level 22 between the two-layer hard raw material of wood-charcoal bed of material 21.
The area of the contact-making surface between described negative current collector 10, lithium metal level 22 and the hard raw material of wood-charcoal bed of material 21 equates.
The described hard raw material of wood-charcoal bed of material 21 is resin carbon-coating, organic polymer pyrolytic carbon layer or starch base pyrolytic carbon layer.
The described hard raw material of wood-charcoal bed of material 21 is the starch base pyrolytic carbon layer.
The thickness of described negative current collector 10 is 16 microns.
The thickness of described lithium metal level 22 is 2 microns.
The thickness of the described hard raw material of wood-charcoal bed of material 21 is 57 microns.
Embodiment 6
The utility model lithium ion secondary battery negative pole and the preparation method who adopts the lithium rechargeable battery of this negative pole:
A kind of lithium rechargeable battery; Comprise battery case, aluminum plastic film pouch, pole piece, positive pole ear, negative lug; Described pole piece is followed successively by negative electrode layer, membrane layer, positive electrode layer and membrane layer from inside to outside; It is characterized in that: described negative electrode layer is a 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 of being made up of the hard raw material of wood-charcoal bed of material and lithium metal level, and described negative electrode material layer is the two-layer hard raw material of wood-charcoal bed of material of outside and the lithium metal level between the two-layer hard raw material of wood-charcoal bed of material.
Described lithium metal level capacitance equates with the total electric irreversible capacity of the two-layer hard raw material of wood-charcoal bed of material.
The described hard raw material of wood-charcoal bed of material is to be formed by hard raw material of wood-charcoal material, conductive agent, binding agent and solvent.
Described hard raw material of wood-charcoal material is that the starch base RESEARCH OF PYROCARBON is processed by common process.
The proportioning of above-mentioned hard raw material of wood-charcoal material, conductive agent, binding agent and solvent is: hard raw material of wood-charcoal material 30～50%, conductive agent 0.5～3%, binding agent 0.5～3%, solvent 44～69%.
Above-mentioned hard raw material of wood-charcoal material is that resin carbon, organic polymer RESEARCH OF PYROCARBON or starch base RESEARCH OF PYROCARBON are processed by common process.
Above-mentioned resin carbon is phenolic resins, epoxy resin or poly furfuryl alcohol PFA-C; The organic polymer RESEARCH OF PYROCARBON is PFA, PVC, PVDF or PAN; The starch base RESEARCH OF PYROCARBON is rice starch, cornstarch, sorghum starch, wheaten starch tapioca, sweet potato starch or farina.
Described positive electrode layer is the conventional positive pole in this area, comprises plus plate current-collecting body, loads on the positive electrode material layer on the plus plate current-collecting body.
Above-mentioned positive electrode material layer is to be formed by positive electrode, conductive agent, binding agent and solvent.
Positive electrode of the present invention is cobalt acid lithium (LiCoO
2).
The proportioning of above-mentioned positive electrode, conductive agent, binding agent and solvent is: hard raw material of wood-charcoal material 40～60%, conductive agent 0.5～5%, binding agent 0.5～5%, solvent 25～59%.
Above-mentioned positive electrode is the various positive electrodes that well known to a person skilled in the art that lithium ion battery is used, comprises 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.
Described barrier film is PP/PE/PP.
Described barrier film 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.
A kind of preparation method of lithium rechargeable battery comprises following processing step:
A, preparation anode sizing agent
The even mixing of positive electrode, conductive agent, bonding agent and solvent obtained anode sizing agent;
B, preparation positive electrode layer
The anode sizing agent that steps A is prepared evenly is coated in the one side or the two sides of plus plate current-collecting body, forms positive electrode material layer, and coating thickness is 100～250 microns, and positive electrode material layer and plus plate current-collecting body form positive electrode layer;
C, preparation cathode size
The even mixing of hard raw material of wood-charcoal material, conductive agent, bonding agent and solvent obtained cathode size;
D, coating cathode size
The cathode size that step C is prepared evenly is coated in the one side or the two sides of negative current collector, forms the hard raw material of wood-charcoal bed of material, and coating thickness is 50～100 microns;
E, plating lithium metal level
In vacuum degree is 0.5 * 10
-2～2 * 10
-2In the vacuum environment of mbar, adopt the method for ion sputtering, the control sputtering current is 10～50mA, and frequency is 50Hz, and the time is 2～10 minutes, and lithium evenly is plated in the hard raw material of wood-charcoal bed of material surface among the step D, and thickness is 0.5～3 micron;
F, preparation negative electrode layer
In inert atmosphere; The cathode size that step C is prepared evenly is coated in the lithium layer on surface of metal in the step e; Form the hard raw material of wood-charcoal bed of material; Coating thickness is 50～100 microns, and the two-layer hard raw material of wood-charcoal bed of material 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, preparation pole piece
According to the order that is followed successively by negative electrode layer, membrane layer, positive electrode layer and membrane layer from inside to outside, adopt common process to reel in positive electrode layer, negative electrode layer and barrier film, process pole piece;
H, heat-sealing
Adopt method known in those skilled in the art, the pole piece that step G processes is put into aluminum plastic film pouch and heat-sealing, process electric core;
I, fluid injection
Adopt method known in those skilled in the art, inject the electrolyte in the step H gained electricity core and leave standstill;
J, once change into
Adopt method known in those skilled in the art, the electric core after the 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, promptly obtains final lithium rechargeable battery product.
Coating thickness described in the step B is 150～200 microns.
Coating thickness described in the step D is 70～90 microns.
Described in the step I inject the electrolyte in the step H gained electricity core and leave standstill be meant at first be evacuated to vacuum degree >=-85kPa, fluid injection under 0.1～0.3MPa is then left standstill 3～15min at last and is accomplished fluid injection.
Once changing into described in the step J handled the electric current that is meant employing 0.05C electric core is charged to the 70%SOC state.
The capacity that tests out battery described in the step K 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.
Said inert atmosphere is any inert gas that this area is known altogether, is preferably argon gas or nitrogen.
Said electrolyte is for containing lithium salts and nonaqueous solvents, and said lithium salts can be in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl sulfonic acid lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and the lithium iodide one or more; Said nonaqueous solvents can be fluorine-containing for gamma-butyrolacton, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, acid anhydrides, N-NMF, N-methylacetamide, acetonitrile, sulfolane, methyl-sulfoxide, dimethyl sulfite and other, in the ring-type organic ester of sulfur-bearing or unsaturated bond one or more; The concentration of said lithium salts in electrolyte can be 0.3～4 mol, is preferably 0.5～2 mol.
Claims (9)
1. lithium ion secondary battery negative pole; Comprise negative current collector (10); It is characterized in that: described lithium ion secondary battery negative pole is a layer structure; Described negative current collector (10) one side or two sides are bonded with the negative electrode material layer of being made up of the hard raw material of wood-charcoal bed of material (21) and lithium metal level (22) (20), and described negative electrode material layer (20) is the two-layer hard raw material of wood-charcoal bed of material (21) of outside and the lithium metal level (22) between the two-layer hard raw material of wood-charcoal bed of material (21).
2. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: in the described negative electrode material layer (20) near the hard raw material of wood-charcoal bed of material (21) of negative current collector (10) one sides and tight contact bonding with negative current collector (10).
3. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the described two-layer hard raw material of wood-charcoal bed of material (21) closely contacts with lithium metal level (22) between the two-layer hard raw material of wood-charcoal bed of material (21).
4. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the area of the contact-making surface between described negative current collector (10), lithium metal level (22) and the hard raw material of wood-charcoal bed of material (21) equates.
5. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the described hard raw material of wood-charcoal bed of material (21) is resin carbon-coating, organic polymer pyrolytic carbon layer or starch base pyrolytic carbon layer.
6. according to claim 1 or 5 described a kind of lithium ion secondary battery negative poles, it is characterized in that: the described hard raw material of wood-charcoal bed of material (21) is the starch base pyrolytic carbon layer.
7. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the thickness of described negative current collector (10) is 8～20 microns.
8. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the thickness of described lithium metal level (22) is 0.5～3 micron.
9. a kind of lithium ion secondary battery negative pole according to claim 1 is characterized in that: the thickness of the described hard raw material of wood-charcoal bed of material (21) is 50～100 microns.
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|---|---|---|---|
| CN2012202561172U CN202616342U (en) | 2012-06-01 | 2012-06-01 | Lithium-ion secondary battery negative pole |
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|---|---|---|---|
| CN2012202561172U CN202616342U (en) | 2012-06-01 | 2012-06-01 | Lithium-ion secondary battery negative pole |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888194A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | The preparation method of graphene/silicon/carbon composite sandwich electrode |
| CN112335073A (en) * | 2018-07-06 | 2021-02-05 | 株式会社Lg化学 | Negative electrode for lithium secondary battery, method of pre-lithiating the negative electrode, and lithium secondary battery including the negative electrode |
| CN112825350A (en) * | 2019-11-20 | 2021-05-21 | 郑州宇通集团有限公司 | Pre-lithiation negative pole piece, preparation method thereof and lithium secondary battery |
-
2012
- 2012-06-01 CN CN2012202561172U patent/CN202616342U/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335073A (en) * | 2018-07-06 | 2021-02-05 | 株式会社Lg化学 | Negative electrode for lithium secondary battery, method of pre-lithiating the negative electrode, and lithium secondary battery including the negative electrode |
| US12113203B2 (en) | 2018-07-06 | 2024-10-08 | Lg Energy Solution, Ltd. | Negative electrode for lithium secondary battery, method for pre-lithiation thereof, and lithium secondary battery including same |
| CN109888194A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | The preparation method of graphene/silicon/carbon composite sandwich electrode |
| CN112825350A (en) * | 2019-11-20 | 2021-05-21 | 郑州宇通集团有限公司 | Pre-lithiation negative pole piece, preparation method thereof and lithium secondary battery |
| CN112825350B (en) * | 2019-11-20 | 2022-07-26 | 郑州宇通集团有限公司 | Pre-lithiation negative pole piece, preparation method thereof and lithium secondary battery |
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