WO2011077656A1 - リチウムイオン二次電池用負極 - Google Patents
リチウムイオン二次電池用負極 Download PDFInfo
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- WO2011077656A1 WO2011077656A1 PCT/JP2010/007171 JP2010007171W WO2011077656A1 WO 2011077656 A1 WO2011077656 A1 WO 2011077656A1 JP 2010007171 W JP2010007171 W JP 2010007171W WO 2011077656 A1 WO2011077656 A1 WO 2011077656A1
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- WIPO (PCT)
- Prior art keywords
- active material
- containing silane
- alkoxy group
- binder
- resin
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000011149 active material Substances 0.000 claims abstract description 125
- 239000011230 binding agent Substances 0.000 claims abstract description 64
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 53
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 15
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920001721 polyimide Polymers 0.000 claims description 11
- 239000009719 polyimide resin Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 239000004432 silane-modified polyurethane Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000126 substance Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229920005575 poly(amic acid) Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000002482 conductive additive Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000003273 ketjen black Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
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- 238000003980 solgel method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KVMAQXBSRFDBSI-UHFFFAOYSA-N 2-methoxyethoxy(dimethyl)silane Chemical compound COCCO[SiH](C)C KVMAQXBSRFDBSI-UHFFFAOYSA-N 0.000 description 1
- ZBSKZKPSSKTLNE-UHFFFAOYSA-N 4-methylpent-3-enoxysilane Chemical compound CC(=CCCO[SiH3])C ZBSKZKPSSKTLNE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
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- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
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- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- WPJVMPQSTHTWKF-UHFFFAOYSA-N ethoxy-dimethoxy-methylsilane Chemical compound CCO[Si](C)(OC)OC WPJVMPQSTHTWKF-UHFFFAOYSA-N 0.000 description 1
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a negative electrode for a lithium ion secondary battery.
- a secondary battery is one that extracts chemical energy of a positive electrode active material and a negative electrode active material as electric energy to the outside by a chemical reaction via an electrolyte.
- a secondary battery having a high energy density among the practically used secondary batteries is a lithium ion secondary battery.
- lithium-containing metal composite oxides such as lithium cobalt composite oxide are mainly used as the positive electrode active material, and lithium ion insertion (interlayer of lithium intercalation compounds) is used as the negative electrode active material.
- lithium ion insertion interlayer of lithium intercalation compounds
- Carbon materials having a multilayer structure capable of releasing lithium ions from the formation layer) and the cocoon layer are mainly used.
- the positive and negative electrode plates are manufactured as follows. Each active material, binder resin, and conductive additive are dispersed in a solvent to form a slurry. This slurry is applied on both sides onto a metal foil as a current collector. Next, the solvent contained in the slurry is removed by drying to form a mixture layer on the current collector. Then, the mixture layer and the current collector are compression-molded with a roll press to obtain a positive electrode plate or a negative electrode plate.
- a negative electrode active material having a charge / discharge capacity that greatly exceeds the theoretical capacity of a carbon material has been developed as a negative electrode active material for lithium ion secondary batteries.
- a material containing a metal that can be alloyed with lithium such as Si or Sn is expected.
- Patent Document 1 proposes an electrode for a secondary battery using an alkoxyl group-containing resin as a binder resin.
- JP 2009-43678 A JP 2009-43678 A
- the present invention has been made in view of such circumstances, and even when an active material having a large volume change due to insertion and extraction of lithium is used, the active material is further prevented from being separated from and removed from the current collector. It aims at providing the negative electrode for lithium ion secondary batteries which has the outstanding cycling performance by doing.
- the surface treatment agent has at least one of a methoxy group and a ethoxy group.
- a methoxy group or an ethoxy group becomes a hydroxyl group (OH group) when hydrolyzed. This hydroxyl group reacts with a hydroxyl group present on the surface of the active material. Therefore, it is considered that the surface treatment agent is bonded to the surface of the active material.
- This surface treatment agent is preferably used in an amount of 1% by mass to 10% by mass with respect to 100% by mass of the active material.
- a SiO 2 film can be formed on the surface of the active material. Since SiO 2 is insulative, conductivity is deteriorated, which is not preferable in terms of battery characteristics.
- the surface treatment agent is used in an amount of less than 1% by mass, the effect due to the surface treatment is not observed.
- the hydroxyl group on the surface of the active material reacts with the surface treatment glaze in this way, the active point on the surface of the active material is covered with the surface treatment agent. Therefore, decomposition of the electrolytic solution due to active sites on the surface of the active material can be suppressed.
- the surface treatment agent can form a siloxane bond (—Si—O—Si—) with the binder. Therefore, the active material is well bonded to the binder through the surface treatment agent.
- the binder since the binder contains an alkoxy group-containing silane-modified site, the binder has good adhesion to a current collector and a conductive additive which are inorganic components.
- the binder includes an alkoxy group-containing silane-modified polyimide resin, an alkoxy group-containing silane-modified polyamideimide resin, an alkoxy group-containing silane-modified polyurethane resin, an alkoxy group-containing silane-modified epoxy resin, an alkoxy group-containing silane-modified acrylic resin, and an alkoxy group-containing silane. It is preferably made of any one of modified phenolic resins.
- binders are all hybrids of a resin and an alkoxy group-containing silane-modified site.
- the active material and the like are firmly held on the current collector via the binder.
- the active material preferably contains Si.
- the theoretical capacity of carbon used for the active material of the negative electrode is 372 mAhg ⁇ 1
- the theoretical capacity of Si is 4200 mAhg ⁇ 1 .
- Si has a larger theoretical capacity than carbon.
- Si can bind well with the above surface treatment agent. Therefore, Si, the surface treatment agent, and the binder are well bonded, and Si as the active material can be firmly held by the current collector.
- FIG. 1 shows a current collector 1 and an active material layer 6 formed on the current collector 1.
- the active material layer 6 is formed by holding the active material 2 surface-treated with the surface treatment agent and the conductive auxiliary agent 4 on the current collector 1 via the binder 3.
- a surface treatment agent layer 5 is formed on at least a part of the surface of the active material 2 surface-treated with the surface treatment agent .
- FIG. 1 is a schematic diagram, and the size and shape of each substance are not accurate.
- the active material 2 is firmly held on the current collector 1 through the surface treatment agent layer 5 and the binder 3. Since the active material 2 is firmly held in the current collector 1 in this way, the active material 2 is removed from the current collector 1 even if the volume of the active material 2 changes due to insertion / extraction of Li during charge / discharge. Peeling and dropping are suppressed.
- the lithium ion secondary battery can exhibit excellent cycle characteristics.
- FIG. 1 is a schematic view illustrating a negative electrode for a lithium ion secondary battery according to the present invention.
- FIG. 2 is a graph showing charge / discharge cycle test results of model batteries using the negative electrodes of Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention, showing the relationship between the number of cycles and the discharge current capacity retention rate.
- FIG. 3 is an enlarged view of FIG.
- FIG. 4 is an explanatory view showing the configuration of the electrode plate group of the laminate type battery.
- the negative electrode for a lithium ion secondary battery of the present invention has a current collector and an active material layer formed on the surface of the current collector.
- a current collector is a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharging or charging.
- the current collector can adopt a shape such as a foil or a plate, but is not particularly limited as long as it has a shape according to the purpose.
- a copper foil or an aluminum foil can be suitably used.
- the conductive additive is added to the active material layer in order to increase the conductivity of the active material layer.
- the conductive auxiliary agent carbon black, graphite, acetylene black, ketjen black, carbon fiber, etc., which are carbon fine particles, can be used alone or in combination of two or more.
- An active material is a substance that directly contributes to electrode reactions such as charge reaction and discharge reaction.
- a material capable of inserting and extracting lithium is used as the negative electrode active material, and for example, a carbon-based material, a metal capable of alloying lithium, or an oxide of the metal is used.
- These active materials can be used alone or in combination of two or more.
- the active material used in the present invention is not particularly limited. However, such an active material is preferably in the form of powder, and the powder particle diameter is preferably 100 ⁇ m or less.
- the active material for example, graphite, Si, Sn, Al, Ag, Zn, Ge, Cd, Pb and oxides of these metals can be preferably used.
- the active material used in the present invention is treated with a surface treatment agent.
- a surface treating agent couple
- the metal or an oxide of the metal tends to have a hydroxide layer on the surface. Accordingly, a metal or an oxide of the metal is preferably used as the active material.
- the active material contains Si.
- Si, SiO, SiO 2 , an alloy containing Si, or an Si compound can be used as the active material.
- n 1, methyltrimethoxysilane, methyltriethoxysilane, methylmethoxydiethoxysilane, methylethoxydimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like can be mentioned.
- n 2
- dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane and the like can be mentioned.
- tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane are preferable as the surface treatment agent.
- Tetramethoxysilane and tetraethoxysilane both become Si (OH) 4 when hydrolyzed, and can then form siloxane bonds in four directions by dehydration condensation. Therefore, tetramethoxysilane and tetraethoxysilane are bonded to the surface of the active material to cover the active material, and at the same time, the active material and the binder can be strongly bonded.
- vinyl trimethoxysilane and vinyltriethoxysilane are polymerized at the time of charge / discharge. Therefore, vinyltrimethoxysilane and vinyltriethoxysilane bonded to the surface of the active material can stabilize the surface state of the active material.
- the methoxy group or ethoxy group is hydrolyzed to become a hydroxyl group.
- the surface treatment agent and the active material are bonded by dehydration condensation of the hydroxyl group of the surface treatment agent with the hydroxyl group of the active material. Thereby, a surface treating agent layer is formed on at least a part of the surface of the active material.
- the method for surface treating the surface treatment agent with an active material is not particularly limited.
- a solution in which a surface treatment agent is dissolved in water or alcohol is prepared, and the above solution is dropped on the active material little by little while stirring the active material. Thereafter, the active material wetted with the surface treatment agent is dried and heat-treated at 80 ° C. to 200 ° C.
- the surface treatment agent layer is formed on at least a part of the surface of the active material by surface-treating the active material with the surface treatment agent.
- the active material needs to be surface-treated before being mixed with a binder or the like. This is because when the active material is surface-treated in advance, the surface treatment agent is easily bonded to the active material.
- the surface treatment agent is preferably used in an amount of 3% by mass to 9% by mass.
- the active material thus surface-treated is held on the current collector by the above-mentioned binder.
- the binder which is a resin having an alkoxy group-containing silane-modified site is an alkoxy group-containing silane-modified polyimide resin, an alkoxy group-containing silane-modified polyamideimide resin, an alkoxy group-containing silane-modified polyurethane resin, an alkoxy group-containing silane-modified epoxy resin, or an alkoxy group-containing resin. It preferably consists of either a silane-modified acrylic resin or an alkoxy group-containing silane-modified phenol resin.
- binders are all hybrids of a resin and an alkoxy group-containing silane-modified site.
- the binder has an alkoxy group-containing silane-modified site. That is, the binder has a sol-gel reaction site structure.
- the sol-gel reaction site structure is a structure that contributes to the reaction when performing the sol-gel method.
- the sol-gel method is the following method. An inorganic or organometallic salt solution is used as a starting solution, and this inorganic or organometallic salt solution is made into a colloidal solution (Sol) by hydrolysis and polycondensation reaction. The colloidal solution (Sol) is further converted to a solid (Gel) that has lost fluidity by further promoting the reaction.
- the binder has the sol-gel reaction site structure described above, various reactions occur between the sol-gel reaction sites, the sol-gel reaction site and the hydroxyl group of the resin, the sol-gel reaction site and the hydroxyl group of the surface treatment agent, etc., when the resin is cured. .
- the hydroxyl group of the surface treatment agent reacts with the alkoxy group-containing silane-modified site of the above-described binder to form a siloxane bond (—Si—O—Si—). Therefore, the active material is firmly held on the current collector via the binder.
- Each of the above binders can be synthesized by a known technique.
- an alkoxy group-containing silane-modified polyimide resin can be formed by reacting a precursor, a polyamic acid composed of a carboxylic anhydride component and a diamine component, and an alkoxysilane partial condensate.
- a precursor a polyamic acid composed of a carboxylic anhydride component and a diamine component
- an alkoxysilane partial condensate a product obtained by partially condensing a hydrolyzable alkoxysilane monomer in the presence of an acid or base catalyst and water can be used.
- the alkoxy group-containing silane-modified polyimide resin can also be obtained by curing an alkoxy group-containing silane-modified polyamic acid resin.
- the alkoxy group-containing silane-modified polyamic acid resin can be prepared by previously reacting an alkoxysilane partial condensate with an epoxy soot compound to form an epoxy group-containing alkoxysilane partial condensate, and then reacting with a polyamic acid.
- a commercial item can be used suitably as said binder.
- the trade name “COMPOCERAN E” manufactured by Arakawa Chemical Industries
- the trade name “COMPOCELAN” which is an alkoxy group-containing silane-modified acrylic resin.
- an alkoxy group-containing silane-modified polyimide resin has a structure represented by the following (Chemical Formula 1).
- the binder is used as a binder when fixing the active material and conductive aid to the current collector.
- the binder is required to bind the active material or the like in as small an amount as possible.
- the amount of the binder is desirably 1% by mass to 40% by mass.
- the method for producing a soot for a negative electrode for a lithium ion secondary battery of the present invention is not particularly limited.
- a general manufacturing method can be used as the manufacturing method.
- the following method can be used.
- An active material treated with a surface treating agent, a binder, and a conductive additive are dispersed in a solvent to form a slurry, which is applied onto a current collector. Then, the applied binder is cured to hold the active material and the conductive additive treated with the surface treating agent on the current collector.
- Coating means placing a binder, a surface-treated active material, and a conductive aid on a current collector.
- a coating method a coating method generally used when producing a reed battery electrode such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method can be used.
- a binder, a surface-treated active material, and a conductive additive are mixed in advance, and a solvent is added to the mixture to form a slurry, which can be applied to a current collector.
- Usable solvents include N-methyl-2-pyrrolidone (NMP), methanol, methyl isobutyl ketone (MIBK) and the like.
- a general mixing device such as a planetary mixer, a defoaming kneader, a ball mill, a paint shaker, a vibration mill, a reiki machine, and an agitator mill can be used.
- the coating thickness of the slurry is preferably 5 ⁇ m to 40 ⁇ m.
- the mixing ratio of the surface-treated active material, the binder carrier, and the conductive auxiliary agent is 100% by mass (wt%) of the total of the surface-treated active material, the binder, and the conductive auxiliary agent.
- the active material: conducting aid: binder 40: 40: 20 to 90: 5: 5 (mass% (wt%)) is preferable.
- this mixing ratio shows the upper limit and the lower limit of each.
- the upper limit is 90% by mass and the lower limit is 40% by mass.
- the curing of the binder may be performed under curing conditions according to the binder used. Further, when the binder is cured, a sol-gel curing reaction is also caused by the alkoxy group-containing silane-modified site of the binder. Since the resin that has undergone sol-gel curing habit reaction has a fine gelled silica site structure (high-order network structure of siloxane bonds), it has good adhesion to the surface-treated active material, conductive additive, and current collector.
- the negative electrode for a lithium ion secondary battery of the present invention was prepared as follows, and a charge / discharge cycle test was performed using a model battery for evaluation. In the test, a laminated cell type battery having a negative electrode as an evaluation electrode was used.
- ⁇ Surface treatment of active material As a negative electrode active material, a commercially available Si powder having a purity of 99.9% or more (manufactured by Fukuda Metals, maximum particle size of 10 ⁇ m or less and average particle size of about 2 ⁇ m) (hereinafter referred to as Si) was prepared. Tetraethoxysilane (manufactured by Shin-Etsu Chemical, KBE-04) and vinyltriethoxysilane (manufactured by Shin-Etsu Chemical, KBE-1003) were prepared as surface treatment agents. The surface treatment was performed according to the method described above.
- Treated active material A was obtained by surface treatment using 9% by mass of tetraethoxysilane with respect to 100% by mass of Si.
- a treatment active material B was obtained by surface treatment using 9% by mass of vinyltriethoxysilane with respect to 100% by mass of Si.
- a treatment active material C was obtained by surface-treating 3 mass% of tetraethoxysilane with respect to 100 mass% of Si.
- a treatment active material D was obtained by surface treatment using 3% by mass of vinyltriethoxysilane with respect to 100% by mass of Si.
- the above-described treated active materials A to D and non-surface-treated Si are used, and an alkoxy group-containing silane-modified polyamic acid resin having a structure shown in (Chemical Formula 1) as a binder (solvent composition: N, N -Dimethylacetamide (DMAc), cured residue 15.1%, viscosity 5100 mPa ⁇ s / 25 ° C, silica in cured residue, 2 wt%, polyimide resin (Arakawa Chemical) and polyvinylidene fluoride (PVDF) (Kureha) Were used, and KB (Ketjen Black) (average particle size: 30 to 50 nm) manufactured by Ketjen Black International Co., Ltd. was used as a conductive additive.
- solvent composition N, N -Dimethylacetamide (DMAc)
- cured residue 15.1% viscosity 5100 mPa ⁇ s / 25 ° C
- silica in cured residue 2
- Example 1 80 wt% of treatment active material A is added to 15 wt% of a paste in which an alkoxy group-containing silane-modified polyamic acid resin is dissolved in N-methylpyrrolidone (NMP), and 5 wt% of ketjen black (KB) is added and mixed. A slurry was prepared.
- NMP N-methylpyrrolidone
- KB ketjen black
- the obtained sheet was dried at 80 ° C. for 20 minutes to volatilize and remove NMP and the like. Thereafter, the current collector made of the copper foil and the negative electrode active material layer made of the alkoxy group-containing silane-modified polyamic acid resin, the treatment active material A, and the ketjen black were firmly adhered and bonded by a roll press. By this tight bonding, adjustment was also performed so that the density of the negative electrode active material layer was 1.2 g / cm 3 .
- Example 1 This was extracted in a substantially rectangular shape (26 mm ⁇ 31 mm) and heated in a vacuum furnace at 350 ° C. for 1 hour to cure the binder, whereby the electrode of Example 1 was obtained.
- Example 2 An electrode of Example 2 was obtained in the same manner as Example 1 except that the treatment active material B was used instead of the treatment active material A as the active material.
- Example 3 An electrode of Example 3 was obtained in the same manner as in Example 1 except that the treatment active material C was used instead of the treatment active material A as the active material.
- Example 4 An electrode of Example 4 was obtained in the same manner as Example 1 except that the treatment active material D was used instead of the treatment active material A as the active material.
- Comparative Example 1 An electrode of Comparative Example 1 was obtained in the same manner as Example 1 except that Si powder that was not surface-treated was used instead of the treated active material A as the active material.
- Comparative Example 2 An electrode of Comparative Example 2 was obtained in the same manner as in Example 1 except that a polyimide resin was used instead of the alkoxy group-containing silane-modified polyamic acid resin as a binder.
- Comparative Example 3 Comparative Example as in Example 1 except that Si powder not subjected to surface treatment was used as the active material instead of the treated active material A, and polyimide resin was used as the binder instead of the alkoxy group-containing silane-modified polyamic acid resin. 3 electrodes were obtained.
- Comparative Example 4 Comparative Example 4 in the same manner as in Example 1 except that PVDF was used instead of the alkoxy group-containing silane-modified polyamic acid resin as a binder and the binder curing conditions were heated at 120 ° C. for 6 hours instead of heating at 350 ° C. for 1 hour. Electrode was obtained.
- the electrode 11 includes a sheet-like current collector foil 12 made of a copper foil, and a negative electrode active material layer 13 formed on the surface of the current collector foil 12.
- the current collector foil 12 includes a substantially rectangular (26 mm ⁇ 31 mm) composite material application part 12a and a tab weld part 12b extending from a corner of the composite material application part 12a.
- a negative electrode active material layer 13 is formed on one surface of the composite material application portion 12a.
- the negative electrode active material layer 13 includes an active material, a conductive additive, and a binder.
- the tab 14 made of nickel is resistance-welded to the tab weld 12b of the current collector foil 12. Furthermore, the resin film 15 is adhered to the tab weld portion 12b.
- the laminated battery includes an electrode plate group 10 in which an electrode 11, a counter electrode 16 and a separator 19 are laminated, a laminate film (not shown) that encloses and seals the electrode plate group 10, and a laminate film. And an electrolytic solution injected into the inside.
- the counter electrode 16 includes a substantially rectangular (25 mm ⁇ 30 mm) composite material application portion 16a and a tab weld portion 16b extending from a corner of the composite material application portion 16a, both of which are made of aluminum. Made of foil.
- a positive electrode active material layer is formed on one surface of the composite material application portion 16a.
- An aluminum tab 17 is resistance welded to the tab weld 16b, and a resin film 18 is attached to the tab weld flange 16b.
- a substantially rectangular sheet (27 mm ⁇ 32 mm, thickness 25 ⁇ m) made of polypropylene resin is used.
- the electrode plate group is formed by laminating the composite material application part 12a of the electrode 11, the separator 19, and the composite material application part 16a of the counter electrode 16 so that the negative electrode active material layer and the positive electrode active material layer face each other with the separator 19 therebetween. 10 is configured.
- the electrode plate group 10 is covered with a set of two laminated films, the three sides are sealed, and the electrolyte solution is injected into the bag-like laminated film. Thereafter, by sealing the remaining one side, a laminated battery in which the four sides are hermetically sealed and the electrode plate group 10 and the electrolyte solution are sealed can be obtained. Note that some of the tabs 15 and 17 on both poles extend outward for electrical connection with the outside.
- the electrode prepared above was used as the negative electrode, the LiCoO 2 electrode (capacity 2.2 mAh / cm 2 , electrode density 2.8 g / cm 3 ) manufactured by Piotrek Co. was used as the positive electrode, and 1 mol / l LiPF 6 / ethylene carbonate.
- FIG. 2 is a graph showing the relationship between the number of cycles and the discharge current capacity retention rate (%), which is a result of the charge / discharge cycle test of the model batteries having negative electrodes of Examples 1 to 4 and Comparative Examples 1 to 4.
- FIG. 3 shows an enlarged view of FIG.
- Example 1 is 79.1%
- Example 2 is 75.6%
- Example 3 is 78.9%
- Example 4 is 75.0%
- Example 1 was 70.7%
- Comparative Example 2 was 73.1%
- Comparative Example 3 was 73.2%
- Comparative Example 4 was 8.0%.
- Comparative Example 4 the binder is PVDF, and the discharge current capacity retention rate is rapidly reduced due to insufficient mechanical strength and adhesion.
- Comparative Example 2 and Comparative Example 3 are compared, there is no significant difference. From this, when the binder is a polyimide resin, the effect of the surface treatment agent is not observed.
- Examples 1 to 4 have a higher discharge current capacity retention rate than Comparative Example 1. It is considered that this is because when the active material is treated with the surface treatment agent, the adhesiveness between the binder and the active material is increased, and the active material is prevented from peeling and dropping, and the soot discharge current capacity retention rate is improved. From the comparison between Comparative Example 2 and Comparative Example 3 and the comparison between Examples 1 to 4 and Comparative Example 1, the effect of this surface treatment agent is remarkably exhibited when the binder has an alkoxy group-containing silane-modified site. I understood it.
- a negative electrode was prepared as follows. Using Si powder as the active material, the active material was combined with a binder (alkoxy group-containing silane-modified polyamic acid resin) in advance to prepare a slurry. After applying the slurry to the current collector, a surface treatment agent (tetraethoxysilane) was dropped, and the current collector coated with the slurry wetted with the surface treatment agent was heat-treated.
- a binder alkoxy group-containing silane-modified polyamic acid resin
- the battery characteristics were measured in the same manner as the electrode of Example 1 using the electrode of Comparative Example 5, but the battery characteristics were not improved as compared with Comparative Example 1.
- the active material is combined with a binder and then surface-treated with a surface treatment agent. From this result, it was found that the active material needs to be combined with the binder after being surface-treated with a surface treatment agent in advance.
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Abstract
Description
活物質を表面処理する際には、活物質100質量%に対して、表面処理剤を1質量%~10質量%用いることが好ましい。更に活物質を100質量%とした場合、表面処理剤を3質量%~9質量%用いることが好ましい。
負極活物質として、純度99.9%以上の市販のSi粉末(福田金属製、最大粒子径10μm以下で平均粒子径2μm程度)、(以下Siと称する)を準備した。表面処理剤として、テトラエトキシシラン(信越化学製、KBE-04)と、ビニルトリエトキシシラン(信越化学製、KBE-1003)を準備した。表面処理は先に説明した方法に準じて行った。
負極活物質として、上記した処理 活物質A~Dおよび表面処理されていないSiを用い、バインダーとして(化1)に示した構造を有するアルコキシ基含有シラン変性ポリアミック酸樹脂(溶剤組成:N,N-ジメチルアセトアミド(DMAc)、硬化残分15.1%、粘度5100mPa・s/25℃、硬化残分中のシリカ、2wt%)、ポリイミド樹脂(荒川化学製)およびポリフッ化ビニリデン(PVDF)(クレハ製)を用い、また導電助剤としてケッチェンブラックインターナショナル社製のKB(ケッチェンブラック)(平均粒径:30~50nm)を用いて、電極を作製した。
アルコキシ基含有シラン変性ポリアミック酸樹脂をN-メチルピロリドン(NMP)に溶解させたペースト15wt%に、処理活物質Aを80wt%入れ、さらにケッチェンブラック(KB)5wt%を添加し、混合してスラリ-を調製した。
活物質として処理活物質Aの代わりに処理活物質Bを用いたこと以外は実施例1と同様にして実施例2の電極を得た。
活物質として処理活物質Aの代わりに処理活物質Cを用いたこと以外は実施例1と同様にして実施例3の電極を得た。
活物質として処理活物質Aの代わりに処理活物質Dを用いたこと以外は実施例1と同様にして実施例4の電極を得た。
活物質として処理活物質Aの代わりに表面処理されていないSi粉末を用いたこと以外は実施例1と同様にして比較例1の電極を得た。
バインダーとしてアルコキシ基含有シラン変性ポリアミック酸樹脂の代わりにポリイミド樹脂を用いたこと以外は実施例1と同様にして比較例2の電極を得た。
活物質として処理活物質Aの代わりに表面処理されていないSi粉末を用い、かつバインダーとしてアルコキシ基含有シラン変性ポリアミック酸樹脂の代わりにポリイミド樹脂を用いた以外は実施例1と同様にして比較例3の電極を得た。
バインダーとしてアルコキシ基含有シラン変性ポリアミック酸樹脂の代わりにPVDFを用い、バインダー硬化条件を350℃で1時間加熱する代わりに120℃で6時間加熱したこと以外は実施例1と同様にして比較例4の電極を得た。
図4により、ラミネート型電池の極板群の構成を説明する。上記の手順で作製した電極は図4の電極11に採用する。
図4により、ラミネート型電池の構成を説明する。図4に示すようにラミネート型電池は、電極11、対極16およびセパレータ19が積層されてなる極板群10と、極板群10を包み込んで密閉するラミネートフィルム(図示せず)と、ラミネートフィルム内に注入される電解液と、を備える。
上記で作成した電極を負極とし、パイオトレック社製LiCoO2電極(容量2.2mAh/cm2、電極密度2.8g/cm3)を正極とし、1mol/lのLiPF6/エチレンカ-ボネ-ト(EC)+ ジエチルカ-ボネ-ト(DEC)(EC:DEC=1:1(体積比))溶液200μlを電解液として、上記構成のラミネート型電池を作製した。
このモデル電池における評価極の評価を次の 方法で行った。
充電は、1Cで4.2VまでCCCV充電(定電流定電圧充電)を2.5時間行った。放電は、3.0Vまで1Cの一定電流で放電した(1C、CC放電(定電流放電))。
放電電流容量維持率(%)=(各 サイクルの放電電流容量/1サイクル目の放電電流容量)×100
Claims (4)
- 集電体と、
該集電体の表面に、導電助剤と、一般式:X-Si(CH3)n-(OR)3-n(n=0、1、2)(OR=メトキシ基、またはエトキシ基、X=メトキシ基、エトキシ基、またはビニル基)で示される表面処理剤を用いて表面処理された活物質と、をアルコキシ基含有シラン変性部位を有する樹脂からなるバインダーを介して固定した活物質層と、
を有するリチウムイオン二次電池用負極。 - 前記バインダーは、アルコキシ基含有シラン変性ポリイミド樹脂、アルコキシ基含有シラン変性ポリアミドイミド樹脂、アルコキシ基含有シラン変性ポリウレタン樹脂、アルコキシ基含有シラン変性エポキシ樹脂、アルコキシ基含有シラン変性アクリル樹脂、およびアルコキシ基含有シラン変性フェノール樹脂のいずれかからなる請求項1に記載のリチウムイオン二次電池用負極。
- 前記活物質は、Siを含む請求項1または2に記載のリチウムイオン二次電池用負極。
- 前記表面処理剤は、前記活物質100 質量%に対して、1質量%~10質量%用いられる請求項1~3のいずれかに記載のリチウムイオン二次電池用負極。
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US13/514,856 US20120244435A1 (en) | 2009-12-24 | 2010-12-09 | Negative electrode for lithium-ion secondary battery |
KR1020127012192A KR101388666B1 (ko) | 2009-12-24 | 2010-12-09 | 리튬 이온 2차 전지용 부극 |
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KR20140104268A (ko) | 2013-02-20 | 2014-08-28 | 삼성에스디아이 주식회사 | 전지용 바인더, 이를 채용한 음극과 리튬전지 |
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- 2010-12-09 US US13/514,856 patent/US20120244435A1/en not_active Abandoned
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US20120244435A1 (en) | 2012-09-27 |
KR101388666B1 (ko) | 2014-04-22 |
JP2011134584A (ja) | 2011-07-07 |
JP5120371B2 (ja) | 2013-01-16 |
EP2518796A4 (en) | 2014-04-23 |
EP2518796B1 (en) | 2016-03-09 |
CN102687314A (zh) | 2012-09-19 |
KR20120066669A (ko) | 2012-06-22 |
EP2518796A1 (en) | 2012-10-31 |
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