CN113889621B - Binder, negative electrode and lithium ion battery - Google Patents
Binder, negative electrode and lithium ion battery Download PDFInfo
- Publication number
- CN113889621B CN113889621B CN202010627381.1A CN202010627381A CN113889621B CN 113889621 B CN113889621 B CN 113889621B CN 202010627381 A CN202010627381 A CN 202010627381A CN 113889621 B CN113889621 B CN 113889621B
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- CN
- China
- Prior art keywords
- polyvinyl alcohol
- binder
- modified polyvinyl
- formula
- carboxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011230 binding agent Substances 0.000 title claims abstract description 92
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 159
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 159
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 91
- 239000007773 negative electrode material Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 45
- 229920000768 polyamine Polymers 0.000 claims description 45
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 150000003512 tertiary amines Chemical class 0.000 claims description 15
- 150000003141 primary amines Chemical class 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 10
- -1 hydroxy, amino, carboxy, carbonyl Chemical group 0.000 claims description 7
- 239000006183 anode active material Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims 6
- 150000001412 amines Chemical class 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 10
- 229920006001 poly(vinyl alcohol-co-ethylene) Polymers 0.000 description 10
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 10
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- 230000000694 effects Effects 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229920002873 Polyethylenimine Polymers 0.000 description 8
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- 239000010703 silicon Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
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- 239000006245 Carbon black Super-P Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- 239000003792 electrolyte Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
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- 230000003993 interaction Effects 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- FDDHFCWYCKQKGY-UHFFFAOYSA-N 4-formyl-3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C(O)=C1 FDDHFCWYCKQKGY-UHFFFAOYSA-N 0.000 description 1
- HLHDIWAOQIRETC-UHFFFAOYSA-N 8-formylnaphthalene-1-carboxylic acid Chemical compound C1=CC(C=O)=C2C(C(=O)O)=CC=CC2=C1 HLHDIWAOQIRETC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
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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
- H01M4/62—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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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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Abstract
The invention relates to the field of binders for negative electrode materials of lithium ion batteries, and discloses a binder, a negative electrode and a lithium ion battery, wherein the binder comprises carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer; the carboxyl-modified polyvinyl alcohol has a structure represented by formula (1) or formula (2), and the carboxyl-modified polyvinyl alcohol copolymer has a structure represented by formula (3) or formula (4), wherein x 1 、x 2 、x 3 、x 4 Each independently is a number greater than 0 and less than 0.5, a 1 、a 2 Each independently is a number in the range of 0.1 to 0.5; r is R 1 、R 2 Each independently selected from the group consisting of substituted and unsubstituted- (CH) 2 ) f ‑、
‑CH 2 ‑Y 1 ‑CH 2 -or-CH 2 ‑(CH 2 Y 2 CH 2 ) j ‑CH 2 -. According to the invention, the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer is used for the lithium ion battery, so that the volume change of the negative electrode can be effectively buffered, the electrode structure is kept stable, and the cycle performance of the battery is improved.
Description
Technical Field
The invention relates to the field of binders for negative electrode materials of lithium ion batteries, in particular to a binder, a negative electrode prepared from the binder and a lithium ion battery prepared from the negative electrode.
Background
In recent years, lithium ion batteries are regarded as ideal choices for battery systems for electric vehicles and large energy storage devices by academia and industry. As an important component of the battery, the anode material of the commercial secondary battery is graphite or various carbon materials synthesized by taking graphite as a precursor, but the theoretical specific capacity value is only 372mAh/g, and the requirement of the electric automobile on the battery with high specific capacity can not be met. Therefore, development of a novel and reliable secondary battery anode material becomes a technical bottleneck for development of high-performance secondary batteries.
Silicon, which is the negative electrode material of the secondary battery, has the highest specific mass capacity (about 4200 mAh/g), and is becoming a more desirable negative electrode material of the secondary battery. However, silicon can generate huge volume change in the process of lithium ion intercalation/deintercalation, which easily causes separation of partial silicon particles and a conductive agent or a current collector, so that loss of active substances is caused, further, the capacity of a battery is rapidly attenuated, the cycle stability is deteriorated, and the commercialization application of the battery is restricted.
The binder is an important component of the anode and the cathode of the secondary battery, and plays a role in maintaining the structural integrity of the electrode and ensuring the normal and repeated operation of the battery in the charge and discharge processes. Polyvinylidene fluoride (PVDF) has been mainly used as a binder in research and practical production in the field of lithium ion batteries for a long time, but PVDF bonded to silicon by van der waals force alone is insufficient to provide stable cycle performance. Meanwhile, when PVDF is used as a binder, an organic solvent N-methyl pyrrolidone (NMP) is volatile, inflammable, explosive, high in toxicity and high in recovery cost, and does not meet the requirements of economy and environmental protection. Therefore, aqueous binders are an important direction of development for lithium ion battery binders.
The aqueous binder for the lithium ion battery is mainly as follows: styrene Butadiene Rubber (SBR)/sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), sodium alginate (NaAlg), polyvinyl alcohol (PVA), and the like. SBR is used as a binder, CMC must be added as a thickener at the same time, but CMC is generally viscous, brittle and poor in flexibility, and the pole piece is prone to cracking during charge and discharge. PAA is adopted as a binder, and the polymer has high glass transition temperature and is harder at normal temperature, so that the pole piece prepared from the binder can be broken due to volume change of active substances in the lithium intercalation process, and the active substances fall off from the pole piece. PVA is used as a binder, and the polymer only contains hydroxyl groups, so that strong interaction with a silicon negative electrode cannot be formed, and the polymer is easy to crystallize, so that active substances on a pole piece prepared from the binder are easy to fall off.
Therefore, there is an urgent need to develop a polymer binder having high adhesion and flexibility to maintain the electrode structure stable and to improve the cycle life of the battery.
Disclosure of Invention
The invention aims to solve the problems of unstable electrode structure and poor battery cycle performance of the existing binder, and provides a binder, a negative electrode prepared from the binder and a lithium ion battery prepared from the negative electrode. The binder adopted by the negative electrode is polyvinyl alcohol modified by carboxyl and/or polyvinyl alcohol copolymer modified by carboxyl, and can form strong acting force with the negative electrode active material, so that the volume change of the negative electrode is effectively buffered, the electrical connection and the integrity of the electrode are maintained, the electrode structure is stable, and the cycle performance of the battery is improved.
In order to achieve the above object, the present invention provides in a first aspect a binder comprising a carboxyl-modified polyvinyl alcohol and/or a carboxyl-modified polyvinyl alcohol copolymer; the carboxyl modified polyvinyl alcohol has a structure shown in a formula (1) or a formula (2), the carboxyl modified polyvinyl alcohol copolymer has a structure shown in a formula (3) or a formula (4),
wherein x is 1 、x 2 、x 3 、x 4 Each independently is a number greater than 0 and less than 0.5, a 1 、a 2 Each independently is a number in the range of 0.1 to 0.5; r is R 1 、R 2 Each independently selected from the group consisting of substituted and unsubstituted- (CH) 2 ) f -、
-CH 2 -Y 1 -CH 2 -or-CH 2 -(CH 2 Y 2 CH 2 ) j -CH 2 -, f is an integer of 0 to 6, Y 1 、Y 2 Each independently selected from O, NH or S, j is an integer from 1 to 4;
the substituted groups are each independently selected from halogen, hydroxy, amino, carboxy, carbonyl, cyano, C 1 -C 6 Alkoxy, C 1 -C 6 Alkyl, C of (2) 6 -C 12 Aryl or C of (2) 6 -C 12 Cycloalkyl groups of (a).
The second aspect of the invention provides a negative electrode, which comprises a negative electrode current collector and a negative electrode active material layer on the surface of the current collector, wherein the negative electrode active material layer comprises a negative electrode active material and a binder, and the binder is the binder of the first aspect of the invention.
In a third aspect, the invention provides a lithium ion battery comprising a negative electrode according to the second aspect of the invention.
According to the technical scheme, the carboxyl group is introduced into the polyvinyl alcohol or the polyvinyl alcohol copolymer to obtain the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer with high adhesiveness and flexibility, and when the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer is used as a binder for the negative electrode of the lithium ion battery, the polymer can form a strong acting force with the negative electrode active material particles, so that the volume change of the negative electrode is effectively buffered, the electrode structure is kept stable, and the cycle performance of the battery is improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously mentioned, the present invention provides in a first aspect a binder comprising a carboxyl-modified polyvinyl alcohol and/or a carboxyl-modified polyvinyl alcohol copolymer; the carboxyl modified polyvinyl alcohol has a structure shown in a formula (1) or a formula (2), the carboxyl modified polyvinyl alcohol copolymer has a structure shown in a formula (3) or a formula (4),
wherein x is 1 、x 2 、x 3 、x 4 The molar ratio of the repeating units containing a carboxyl group in the formulae (1), (2), (3) and (4) is a number of more than 0 and less than 0.5, a 1 、a 2 Each independently is a number in the range of 0.1 to 0.5; r is R 1 、R 2 Each independently selected from the group consisting of substituted and unsubstituted- (CH) 2 ) f -、
-CH 2 -Y 1 -CH 2 -or-CH 2 -(CH 2 Y 2 CH 2 ) j -CH 2 -, f is an integer of 0 to 6, Y 1 、Y 2 Each independently selected from O, NH or S, j is an integer from 1 to 4;
the substituted groups are each independently selected from halogen, hydroxy, amino, carboxy, carbonyl, cyano, C 1 -C 6 Alkoxy, C 1 -C 6 Alkyl, C of (2) 6 -C 12 Aryl or C of (2) 6 -C 12 Cycloalkyl groups of (a).
In the present invention, 1 carboxyl group corresponds to 2 hydroxyl groups, that is, x, in the carboxyl-modified polyvinyl alcohol of the structure represented by the formula (1) 1 The mol of the carboxyl group-containing repeating units corresponds to 2X 1 mol of the polyvinyl alcohol repeating units, so that the remaining polyvinyl alcohol repeating units are 1 to 2x 1 . Similarly, for the carboxyl-modified polyvinyl alcohol copolymer of the structure shown in formula (3), 1 carboxyl group corresponds to 2 hydroxyl groups, i.e., x 3 The mol of the repeating units containing carboxyl groups corresponds to that containingWith 2x 3 mol of recurring units of polyvinyl alcohol containing a 1 mol of polyethylene repeating units, the remainder of the polyvinyl alcohol repeating units being 1-a 1 -2x 3 。
The polymer having the structure shown in the formula (1), the structure shown in the formula (2), the structure shown in the formula (3) or the structure shown in the formula (4) is a random polymer.
In the present invention, x 1 、x 2 、x 3 、x 4 The molar ratio of the repeating units containing carboxyl groups to the entire random polymer (carboxyl-modified polyvinyl alcohol or carboxyl-modified polyvinyl alcohol copolymer) is shown. The method is obtained by measuring a hydrogen spectrum nuclear magnetic spectrum diagram of carboxyl modified polyvinyl alcohol or carboxyl modified polyvinyl alcohol copolymer and calculating (the solvent used for nuclear magnetic testing is deuterated heavy water). a, a 1 、a 2 The molar ratio of the polyethylene segment to the entire random polymer (carboxyl-modified polyvinyl alcohol copolymer) is shown.
The invention is described in
The bond site may be any two sites on benzene, naphthalene, biphenyl, cyclohexane or dicyclohexyl.
In some embodiments of the invention, the- (CH) 2 ) f The selection range is relatively wide, preferably the- (CH) 2 ) f -is absent or selected from-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -one of the following. The invention is described as- (CH) 2 ) f The absence means that f is 0, and when f is 0, the structure of formula (1) is
The structure shown in the formula (2) is +.>
The structure shown in the formula (3) is +.>
The structure shown in the formula (4) is +.>
In some embodiments of the invention, preferably, the-CH 2 -Y 1 -CH 2 -is selected from-CH 2 -O-CH 2 -、-CH 2 -NH-CH 2 -or-CH 2 -S-CH 2 -; the-CH 2 -(CH 2 Y 2 CH 2 ) j -CH 2 -is selected from-CH 2 -(CH 2 OCH 2 ) j -CH 2 -、-CH 2 -(CH 2 NHCH 2 ) j -CH 2 -or-CH 2 -(CH 2 SCH 2 ) j -CH 2 -wherein j is an integer from 1 to 4.
In some embodiments of the invention, preferably, x 1 、x 2 、x 3 、x 4 Each independently is a number in the range of 0.1 to 0.45 when x 1 、x 2 、x 3 、x 4 When the preferable ranges are respectively satisfied, carboxyl groups on the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer are enough, and a large number of hydrogen bonds can be formed between the carboxyl groups and the anode active material (silicon particles), so that the adhesive has good bonding effect; meanwhile, the polyvinyl alcohol chain segment does not form crystallization or forms a small amount of crystallization, so that the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer has better flexibility at room temperature, thereby being suitable for the volume change of active material particles in the charge and discharge process and being beneficial to improving the cycle performance of the battery. More preferably, when x 1 、x 2 、x 3 、x 4 The number of each of the two components is independently in the range of 0.15-0.4, so that the binder has better binding effect, and the cycle performance of the battery is further improved.
In some embodiments of the invention, preferably, a 1 、a 2 Each independently is a number in the range of 0.1 to 0.3, when a 1 、a 2 When the preferable ranges are respectively satisfied, the crystallinity of the polyvinyl alcohol can be effectively reduced by the polyethylene chain segments, and the polyethylene chain segments are not too much, so that the adhesive has small influence on the adhesive effect, and the adhesive has good adhesive effect.
In some embodiments of the present invention, preferably, the halogen is selected from one of fluorine, chlorine, bromine.
In some embodiments of the invention, preferably, the amine group is selected from C 1 -C 6 Primary amine of C 1 -C 6 Alkyl-substituted secondary or tertiary amines of (a).
In some embodiments of the invention, preferably, the C 1 -C 6 Is selected from methoxy or ethoxy.
In some embodiments of the invention, preferably, the C 1 -C 6 The alkyl group of (a) is selected from methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.
In some embodiments of the invention, preferably, the C 6 -C 12 Is selected from phenyl, naphthyl, or biphenyl.
In some embodiments of the invention, preferably, the C 6 -C 12 Is selected from cyclohexyl or dicyclohexyl.
In some embodiments of the invention, preferably, the binder further comprises a polyamine compound.
In some embodiments of the present invention, preferably, the mass ratio of the carboxyl modified polyvinyl alcohol and/or the carboxyl modified polyvinyl alcohol copolymer to the polyamine may be expressed as a mass ratio of the carboxyl modified polyvinyl alcohol to the polyamine, or a mass ratio of the carboxyl modified polyvinyl alcohol copolymer to the polyamine, or a mass ratio of a mixture of the carboxyl modified polyvinyl alcohol and the carboxyl modified polyvinyl alcohol copolymer to the polyamine. When the mass ratio of the carboxyl modified polyvinyl alcohol and/or the carboxyl modified polyvinyl alcohol copolymer to the polyamine compound is (10:1) - (1:5), enough carboxyl groups in the binder can form hydrogen bonding with the anode active material, so that the binder has good bonding performance, and in addition, the carboxyl groups can also interact with the amino groups, so that the three-dimensional network structure of the binder is effectively enhanced, and the rebound resilience and fatigue resistance of the binder are improved. More preferably, when the mass ratio of the carboxyl group-modified polyvinyl alcohol and/or the carboxyl group-modified polyvinyl alcohol copolymer to the polyamine compound is (5:1) - (1:2), the rebound resilience and fatigue resistance of the adhesive can be further improved.
In some embodiments of the present invention, preferably, the polyamine compound contains two or more amine groups. When the polyamine compound contains more than two amine groups, the polyamine compound and the carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer can form a plurality of action sites to form a three-dimensional network structure, and the three-dimensional network structure can cover the negative electrode active material and prevent the negative electrode from irreversibly sliding and buffer the volume change of the negative electrode, so that the stability of the electrode structure is maintained, and the cycle performance of the battery is improved.
In some embodiments of the present invention, preferably, the polyamine compound contains a structural unit selected from at least one of a structure represented by formula (5), a structure represented by formula (6), a structure represented by formula (7), and a structure represented by formula (8), and more preferably, a structure represented by formula (5);
wherein n is 1 、n 2 、n 3 、n 4 Each independently is an integer from 2 to 100000.
In the invention, the structure shown in the formula (5) contains primary amine, secondary amine and tertiary amine at the same time; the structure shown in the formula (6) only contains primary amine; the structure shown in the formula (7) only contains secondary amine, but is acidified by hydrochloric acid during preparation, so that the structure is equivalent to the secondary amine with HCl; the structure of formula (8) contains only tertiary amine.
Wherein, the compound formed by substituting one hydrogen atom in the ammonia molecule with a hydrocarbon group is called primary amine, and has a general formula of RNH 2 . Compounds in which two hydrogen atoms in the ammonia molecule are substituted by hydrocarbon radicals, referred to as secondary amines, of the formula R 2 NH. Compounds in which three hydrogen atoms in the ammonia molecule are replaced by hydrocarbon radicals, referred to as tertiary amines, of the formula R 3 N。
In the invention, when the polyamine compound comprises a structure shown in a formula (5) and at least one selected from the structure shown in a formula (6), the structure shown in a formula (7) and the structure shown in a formula (8), the amino group on the polyamine compound can form a hydrogen bond and/or an electrostatic effect with the carboxyl group on the carboxyl modified polyvinyl alcohol and/or the carboxyl modified polyvinyl alcohol copolymer, so that the three-dimensional network structure of the binder can be further enhanced, the rebound resilience and fatigue resistance of the binder are improved, the active material particles are prevented from irreversibly slipping, and the volume change of the negative electrode is buffered. Preferably, when the polyamine-based compound is selected from the structures represented by the formula (5), since the compound is a branched polymer having a three-dimensional structure, it can more sufficiently form a three-dimensional network structure with the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer.
In some embodiments of the present invention, preferably, the polyamine compound comprises a tertiary amine: secondary amine: the molar ratio of the primary amine is (0.1-0.3): (0.4-0.8): (0.1-0.3). When the mole ratio of the tertiary amine to the secondary amine to the primary amine meets the above range, the static electricity and hydrogen bond effect formed by the polyamine compound and the carboxyl modified polyvinyl alcohol and/or the carboxyl modified polyvinyl alcohol copolymer can effectively strengthen the three-dimensional network structure of the binder, improve the rebound resilience and fatigue resistance of the binder, prevent the active material particles from irreversibly slipping and buffer the volume change of the negative electrode. More preferably, when the tertiary amine: secondary amine: the molar ratio of the primary amine is (0.15-0.25): (0.5-0.7): (0.15-0.25), the three-dimensional network structure of the adhesive can be better enhanced, and the rebound resilience and fatigue resistance of the adhesive can be improved.
In the invention, the structure shown in the formula (5) is branched polyethyleneimine, and the weight average molecular weight of the branched polyethyleneimine is 10 ten thousand-80 ten thousand. The structure shown in the formula (6) is linear polyethylenimine, and the weight average molecular weight of the linear polyethylenimine is 0.1 ten thousand-5 ten thousand. The structure shown in the formula (7) is polyallylamine, and the weight average molecular weight of the polyallylamine is 5 ten thousand to 20 ten thousand. The structure shown in the formula (8) is poly-N, N-dimethylaminoethyl acrylate, and the weight average molecular weight of the poly-N, N-dimethylaminoethyl acrylate is 10 ten thousand-25 ten thousand.
In the invention, the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer is prepared by mixing polyvinyl alcohol or the polyvinyl alcohol copolymer with a compound with a structure shown in a formula (9) or a formula (10), cooling the reaction system to room temperature after the reaction is finished, dripping the cooled solution into an organic solvent to generate a precipitate, and finally sequentially filtering, washing and drying the precipitate;
wherein R is 1 、R 2 Is defined as set forth in the preceding description of the invention.
In some embodiments of the present invention, preferably, the compound containing the structure represented by formula (9) is selected from 2-carboxybenzaldehyde, 3-carboxybenzaldehyde, 4-carboxybenzaldehyde, glyoxylic acid, glutarimide, 8-formyl-1-naphthoic acid, 2-fluoro-5-aldehyde benzoic acid or 4-formyl-3-hydroxybenzoic acid.
In some embodiments of the present invention, preferably, the compound containing the structure represented by formula (10) is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, succinic acid, diglycolic acid, phthalic acid, or trimellitic acid.
In some embodiments of the present invention, preferably, the polyvinyl alcohol is selected from the group consisting of having a degree of hydrolysis of 80%, 87-90%, or99% of polyvinyl alcohol. The weight average molecular weight of the polyvinyl alcohol is 5 ten thousand to 50 ten thousand, more preferably 10 ten thousand to 25 ten thousand. The polyvinyl alcohol may be a polymer containing a structural unit represented by the formula
Wherein the hydroxyl can be used for reacting with carboxyl to realize modification of polyvinyl alcohol. The polyvinyl alcohol is commercially available, for example, from sigma.
In some embodiments of the present invention, preferably, the polyvinyl alcohol copolymer is selected from poly (vinyl alcohol-co-ethylene) copolymers. The poly (vinyl alcohol-co-ethylene) copolymer has the structural formula as described below
The weight average molecular weight of the poly (vinyl alcohol-co-ethylene) copolymer is 5 to 50 tens of thousands, more preferably 10 to 20 tens of thousands. The poly (vinyl alcohol-co-ethylene) copolymer is commercially available, for example, from sigma.
In some embodiments of the invention, preferably, the conditions of the mixing reaction include: the temperature is 50-100deg.C, and the time is 12-72 hr.
In some embodiments of the present invention, the organic solvent is not particularly limited, and organic solvents existing in the art may be used, and preferably, the organic solvent is selected from alcohol, ether or ketone organic solvents. The alcohol organic solvent is at least one selected from methanol, ethanol, isopropanol and tert-butanol. The ether organic solvent is at least one selected from diethyl ether, propyl ether and butyl ether. The ketone organic solvent is selected from at least one of acetone, butanone and pentanone.
In some embodiments of the present invention, preferably, the drying is vacuum drying, and conditions of the vacuum drying include: the drying temperature is 50-80 ℃ and the drying time is 4-20 hours.
The second aspect of the invention provides a negative electrode, which comprises a negative electrode current collector and a negative electrode active material layer on the surface of the current collector, wherein the negative electrode active material layer comprises a negative electrode active material and a binder, and the binder is the binder of the first aspect of the invention.
In some embodiments of the present invention, it is preferable that the content of the binder in the anode active material layer is 5 to 40wt%. The negative electrode active material layer also comprises a silicon-based active material and a conductive agent, wherein the content of the silicon-based active material is 20-90wt%, and the content of the conductive agent is 5-40wt%. The above content ranges are based on the total weight of the anode active material layer.
In some embodiments of the present invention, preferably, the silicon-based active material is selected from a silicon-based material or a silicon-carbon composite based on a silicon-based material.
In some embodiments of the present invention, preferably, the silicon-based material is selected from at least one of nano silicon, micro silicon, porous silicon, amorphous silicon, and silicon oxide.
In some embodiments of the present invention, preferably, the silicon-carbon composite based on a silicon-based material is selected from at least one of a silicon-graphite composite, a silicon-graphene composite, a silicon-carbon nanotube composite, a silicon-carbon fiber composite, and a silicon-amorphous carbon composite.
In some embodiments of the present invention, preferably, the conductive agent is selected from at least one of graphite, acetylene black, conductive carbon black (Super P), graphene, carbon fiber, carbon nanotube, and ketjen black.
In some embodiments of the present invention, the preparation method of the negative electrode is not particularly limited, and may be any preparation method existing in the art, and preferably the preparation method of the negative electrode includes:
(i) Mixing and grinding the carboxyl modified polyvinyl alcohol with the structure shown in the formula (1) or the formula (2) and/or the carboxyl modified polyvinyl alcohol copolymer with the structure shown in the formula (3) or the formula (4) and optional polyamine compound (at least one selected from the structure shown in the formula (5), the structure shown in the formula (6), the structure shown in the formula (7) and the structure shown in the formula (8) serving as a binder, a conductive agent and a silicon-based active substance in the presence of water to obtain slurry;
(ii) And coating the slurry on a current collector and drying to obtain the negative electrode.
In some embodiments of the present invention, preferably, in the step (i), the mass ratio of the silicon-based active material to the conductive agent and the binder is (2-9): (0.5-4): (0.5-4).
In some embodiments of the present invention, the manner of grinding is not particularly limited, and it is preferable that grinding is uniform in a mortar.
In some embodiments of the present invention, preferably, in step (ii), the drying is vacuum drying, and the conditions of the vacuum drying include: the temperature is 50-80 ℃ and the time is 2-18 hours.
The conductive agent, the silicon-based active material, the carboxyl-modified polyvinyl alcohol copolymer and the optional polyamine compound are as described above, and are not described in detail herein.
In some embodiments of the present invention, preferably, the negative electrode current collector is a smooth copper foil, a carbon coated copper foil, or a porous copper foil.
In the present invention, when the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer and the polyamine compound are used as the composite binder to prepare the negative electrode, the polyamine compound and the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer may be added separately in the following order: firstly, uniformly mixing an aqueous solution containing carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer, a silicon-based active substance and a conductive agent, then adding an aqueous solution containing polyamine compound into the mixture to form slurry, and then coating the slurry on a current collector and drying to obtain the negative electrode.
In a third aspect, the invention provides a lithium ion battery comprising a negative electrode according to the second aspect of the invention.
The inventors of the present invention have found in the study that the negative electrode structure can be maintained stable and the battery cycle performance can be improved by using the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer as a binder for a lithium ion battery. The reason for this is presumably because the carboxyl group is introduced into the polyvinyl alcohol or the polyvinyl alcohol copolymer, so that a strong hydrogen bond interaction is formed between the binder polymer and the anode active material particles, and the binding effect of the binder is improved. The carboxyl can also form hydrogen bond with hydroxyl on polyvinyl alcohol or polyvinyl alcohol copolymer, so that the binder can construct a cross-linked three-dimensional network structure around the active material particles, thereby effectively preventing the active material particles from irreversibly slipping and buffering the volume change of the negative electrode, further maintaining the electrical connection and integrity of the electrode, and prolonging the service life of the battery. In addition, the introduction of carboxyl can also effectively reduce the crystallinity of the polyvinyl alcohol or the polyvinyl alcohol copolymer, so that the carboxyl modified polyvinyl alcohol or the carboxyl modified polyvinyl alcohol copolymer has good flexibility at room temperature, thereby being capable of adapting to the volume change of active material particles in the charge and discharge processes and improving the cycle performance of the battery.
The inventor of the present invention also found in the research that the carboxyl modified polyvinyl alcohol and/or the carboxyl modified polyvinyl alcohol copolymer and the polyamine compound are used as the composite binder for the lithium ion battery, so that the stability of the electrode structure can be better maintained, and the cycle performance of the battery can be improved. The reason is presumably that the electrostatic and hydrogen bonding effect is formed between the carboxyl group and the amine group, so that the three-dimensional network structure of the binder is further enhanced, the rebound resilience and fatigue resistance of the binder are improved, and irreversible sliding of the active material particles and buffering of volume change of the negative electrode are prevented. In addition, the carboxyl modified polyvinyl alcohol or the electrostatic and hydrogen bonding effect formed between the carboxyl modified polyvinyl alcohol copolymer and the polyamine compound can be reversibly opened and rebuilt, so that the composite binder can repair mechanical damage, and the cycle performance of the battery is improved.
The present invention will be described in detail by examples. In the examples below, various raw materials used were available from commercial sources without particular explanation.
In the following examples, the binder vs. silicon negative electrode cycle performance was tested by making a CR2025 button cell half-cell, which was tested for charge and discharge cycles.
Polyvinyl alcohol (PVA) is a commercially available product having a weight average molecular weight of 14.6 ten thousand produced by sigma.
Poly (vinyl alcohol-co-ethylene) copolymer (PVA-co-PE) is commercially available from Sigma, inc. having a weight average molecular weight of 13 ten thousand.
Polyallylamine is a commercially available product with a weight average molecular weight of 12 ten thousand produced by the company alfa elsa.
Linear polyethylenimine is a commercially available product produced by the company alfa, which has a weight average molecular weight of 2.5 ten thousand.
Poly-N, N-dimethylaminoethyl acrylate is commercially available from Allatin corporation having a weight average molecular weight of 15 ten thousand.
Branched polyethylenimine-1 is a commercially available product produced by sigma having a weight average molecular weight of 75 ten thousand, wherein the molar ratio of tertiary amine to secondary amine, primary amine is 0.25:0.5:0.25.
branched polyethylenimine-2 is a commercial product produced by sigma having a weight average molecular weight of 75 ten thousand, wherein the molar ratio of tertiary amine to secondary amine, primary amine is 0.1:0.6:0.3.
polyacrylic acid (PAA) is a commercially available product with a weight average molecular weight of 45 ten thousand produced by sigma company.
The nanometer silicon powder is a commercial product produced by the company alfa elsa.
Conductive carbon black (Super P) is a commercially available product produced by the company alfa.
Preparation example 1
This preparation example is used to illustrate the preparation method of carboxyl modified polyvinyl alcohol according to the present invention.
10g of polyvinyl alcohol (weight average molecular weight: 14.6 ten thousand, degree of hydrolysis: 99%) and 5.1g of 4-carboxybenzaldehyde (purchased from alfa aesa corporation) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally filtered, washed and vacuum-dried at 80℃for 12 hours in this order to give a carboxyl-modified polyvinyl alcohol having x of 0.1, designated as 0.1-CPVA-1, having the following structural formula:
preparation example 2
This preparation example is used to illustrate the preparation method of carboxyl modified polyvinyl alcohol according to the present invention.
10g of polyvinyl alcohol (weight average molecular weight: 14.6 ten thousand, degree of hydrolysis: 99%) and 10.2g of 4-carboxybenzaldehyde (purchased from alfa aesa corporation) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally filtered, washed and vacuum-dried at 80℃for 12 hours in this order to give a carboxyl-modified polyvinyl alcohol having x of 0.24, designated as 0.24-CPVA-1, having the following structural formula:
preparation example 3
This preparation example is used to illustrate the preparation method of carboxyl modified polyvinyl alcohol according to the present invention.
10g of polyvinyl alcohol (weight average molecular weight: 14.6 ten thousand, degree of hydrolysis: 99%) and 17g of 4-carboxybenzaldehyde (purchased from alfa eastern company) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the above reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally filtered, washed and vacuum-dried at 80℃for 12 hours in sequence to give a carboxyl-modified polyvinyl alcohol having x of 0.4, designated as 0.4-CPVA-1, having the following structural formula:
preparation example 4
This preparation example is used to illustrate the preparation method of carboxyl modified polyvinyl alcohol according to the present invention.
10g of polyvinyl alcohol (weight average molecular weight: 14.6 ten thousand, degree of hydrolysis: 99%) and 18.8g of terephthalic acid (purchased from alfa eastern company) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally filtered, washed and vacuum-dried at 80℃for 12 hours in sequence to give a carboxyl-modified polyvinyl alcohol having x of 0.4, designated as 0.4-CPVA-2, having the following structural formula:
preparation example 5
This preparation example is used to illustrate the preparation method of the carboxyl modified polyvinyl alcohol copolymer of the present invention.
10g of a poly (vinyl alcohol-co-ethylene) copolymer (weight average molecular weight: 13 ten thousand) and 7.5g of 4-carboxybenzaldehyde (purchased from alfa aesa) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally sequentially filtered, washed and vacuum-dried at 80℃for 12 hours to give a carboxyl-modified polyvinyl alcohol copolymer having x of 0.17 and a of 0.27, designated as 0.17-CPVA-co-PE-1, and the structural formula was as follows:
preparation example 6
This preparation example is used to illustrate the preparation method of the carboxyl modified polyvinyl alcohol copolymer of the present invention.
10g of a poly (vinyl alcohol-co-ethylene) copolymer (weight average molecular weight: 13 ten thousand) and 16.6g of terephthalic acid (available from alfa eastern Corp.) were mixed and reacted at 80℃for 24 hours, after the reaction was completed, the reaction system was cooled to room temperature, and then the cooled solution was dropped into ethanol to produce a precipitate, which was finally filtered, washed and vacuum-dried at 80℃for 12 hours to give a carboxyl-modified polyvinyl alcohol copolymer having x of 0.3 and a of 0.27, designated as 0.3-CPVA-co-PE-2, and having the following structural formula:
example 1
Nano silicon powder, conductive carbon black (Super-P) and a binder (carboxyl modified polyvinyl alcohol prepared in preparation example 1 and recorded as 0.1-CPVA-1) are mixed according to the mass ratio of 8:1:1 are dispersed in water, and after grinding uniformly in a mortar, the slurry is coated on a copper foil by a coater, and the thickness of the coated slurry is 100 μm. Then airing at room temperature, cutting into wafers with the diameter of 13mm by using a slicing machine, then placing the wafers into a vacuum drying oven with the temperature of 80 ℃ for drying for 12 hours, and taking out when the temperature is reduced to room temperature after drying, thus obtaining the nano silicon negative electrode. Transfer the nano-silicon negative electrode into a glove box filled with argon (content O 2 ≤0.5ppm、H 2 O is less than or equal to 0.5 ppm), the nano silicon negative plate is weighed piece by piece in a glove box, the weighed mass is recorded, and then a metal lithium plate is taken as a counter electrode, and 1mol/L LiPF is adopted 6 EC/DMC/DEC (v/v/v=1/1/1) solution as electrolyte, and a CR2025 type button half cell was assembled in a glove box.
Examples 2 to 6
CR2025 type button half-cells were assembled in the same manner as in example 1 except that the binder was replaced with the carboxy-modified polyvinyl alcohol designated 0.24-CPVA-1 prepared in preparation example 2, the carboxy-modified polyvinyl alcohol designated 0.4-CPVA-1 prepared in preparation example 3, the carboxy-modified polyvinyl alcohol designated 0.4-CPVA-2 prepared in preparation example 4, the carboxy-modified polyvinyl alcohol designated 0.17-CPVA-co-PE-1 prepared in preparation example 5, and the carboxy-modified polyvinyl alcohol copolymer designated 0.3-CPVA-co-PE-2 prepared in preparation example 6, respectively.
Example 7
Silica fume, conductive carbon black (Super-P) and a binder (carboxyl-modified polyvinyl alcohol designated as 0.24-CPVA-1 prepared in preparation example 2) were dispersed in water, ground in a mortar for 10-20 minutes, and then polyallylamine was added, wherein the mass ratio of carboxyl-modified polyvinyl alcohol (0.24-CPVA-1) to polyallylamine was 1:1, nanometerThe mass ratio of the silicon powder to the conductive carbon black to the composite binder (carboxyl modified polyvinyl alcohol and polyallylamine) is 8:1:1, a step of; and fully grinding for 10-15 minutes until the slurry is uniform, and coating the slurry on the copper foil by using a coating machine, wherein the thickness of the coated slurry is 100 mu m. Then airing at room temperature, cutting into wafers with the diameter of 13mm by using a slicing machine, then placing the wafers into a vacuum drying oven with the temperature of 80 ℃ for drying for 12 hours, and taking out when the temperature is reduced to room temperature after drying, thus obtaining the nano silicon negative electrode. Transfer the nano-silicon negative electrode into a glove box filled with argon (content O 2 ≤0.5ppm、H 2 O is less than or equal to 0.5 ppm), the nano silicon negative plate is weighed piece by piece in a glove box, the weighed mass is recorded, and then a metal lithium plate is taken as a counter electrode, and 1mol/L LiPF is adopted 6 EC/DMC/DEC (v/v/v=1/1/1) solution as electrolyte, and a CR2025 type button half cell was assembled in a glove box.
Examples 8 to 11
A CR2025 type button half cell was assembled by the same method as in example 7, except that polyallylamine was replaced with linear polyethylenimine, poly N, N-dimethylaminoethyl acrylate, branched polyethylenimine-1 and branched polyethylenimine-2, respectively.
Example 12
A CR2025 type button half cell was assembled in the same manner as in example 10, except that the mass ratio of carboxyl-modified polyvinyl alcohol (0.24-CPVA-1) to branched polyethylenimine-1 was changed to 1:3.
example 13
A CR2025 type button half cell was assembled in the same manner as in example 10 except that the binder (carboxy-modified polyvinyl alcohol designated 0.4-CPVA-1 prepared in preparation example 4) was replaced with the binder (carboxy-modified polyvinyl alcohol designated 0.24-CPVA-1 prepared in preparation example 2).
Example 14
A CR2025 type button half cell was assembled in the same manner as in example 10 except that the binder (carboxyl-modified polyvinyl alcohol designated 0.24-CPVA-1 prepared in preparation example 2) was replaced with the binder (carboxyl-modified polyvinyl alcohol designated 0.17-CPVA-co-PE-1 prepared in preparation example 5).
Example 15
A CR2025 type button half cell was assembled in the same manner as in example 10 except that the binder (carboxyl-modified polyvinyl alcohol designated 0.24-CPVA-1 prepared in preparation example 2) was replaced with the binder (carboxyl-modified polyvinyl alcohol designated 0.3-CPVA-co-PE-2 prepared in preparation example 6).
Comparative examples 1 to 8
CR2025 type button half cell was assembled by the same method as in example 1, except that the binder (carboxy-modified polyvinyl alcohol, denoted as 0.1-CPVA-1, prepared in preparation example 1) was replaced with polyacrylic acid (PAA), polyvinyl alcohol (PVA), poly (vinyl alcohol-co-ethylene) copolymer (PVA-co-PE), polyallylamine, linear polyethylenimine, poly N, N-dimethylaminoethyl acrylate, branched polyethylenimine-1 and branched polyethylenimine-2, respectively.
The batteries prepared in the above examples and comparative examples were subjected to the following performance tests:
the batteries prepared in each example and comparative example were each 10-fold measured in a Land CT 2001C secondary battery performance measuring apparatus at 25.+ -. 1 ℃ by constant current charge-discharge cycle test.
The test conditions were: the discharge cut-off voltage is 0.01V and the charge cut-off voltage is 1.5V, and the charge and discharge cycle is carried out for 3 times under the current density of 100mA/g, and then the charge and discharge cycle is carried out under the current density of 500 mA/g. The test results are shown in Table 1.
TABLE 1
As can be seen from the results of table 1, compared with the polyvinyl alcohol, polyvinyl alcohol copolymer, polyacrylic acid or polyamine compound binder used in the prior art, the carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer used in the invention has better flexibility and cohesiveness, and the carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer is used as the binder, or the carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer is compounded with the polyamine compound to be used as the binder for the lithium ion battery, so that the cycle performance of the battery can be remarkably improved. Further, as can be seen from the test results of comparing the use of the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer as the binder with the use of the carboxyl-modified polyvinyl alcohol and/or the combination of the carboxyl-modified polyvinyl alcohol copolymer and the polyamine compound as the binder, the binder compounded by the carboxyl-modified polyvinyl alcohol and/or the carboxyl-modified polyvinyl alcohol copolymer and the polyamine compound has a significantly better battery cycle performance effect for lithium ion batteries. And, the effect obtained by the adhesive compounded by carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer and branched polyethylenimine is best.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (24)
1. A binder comprising a carboxyl-modified polyvinyl alcohol and/or a carboxyl-modified polyvinyl alcohol copolymer, said binder further comprising a polyamine compound; the carboxyl modified polyvinyl alcohol has a structure shown in a formula (1) or a formula (2), the carboxyl modified polyvinyl alcohol copolymer has a structure shown in a formula (3) or a formula (4),
wherein x is 1 、x 2 、x 3 、x 4 Each independently is a number greater than 0 and less than 0.5, a 1 、a 2 Each independently is a number in the range of 0.1 to 0.5; r is R 1 、R 2 Each independently selected from the group consisting of substituted and unsubstituted- (CH) 2 ) f -、
-CH 2 -Y 1 -CH 2 -or-CH 2 -(CH 2 Y 2 CH 2 ) j -CH 2 -, f is an integer of 0 to 6, Y 1 、Y 2 Each independently selected from O, NH or S, j is an integer from 1 to 4;
the substituted groups are each independently selected from halogen, hydroxy, amino, carboxy, carbonyl, cyano, C 1 -C 6 Alkoxy, C 1 -C 6 Alkyl, C of (2) 6 -C 12 Aryl or C of (2) 6 -C 12 Cycloalkyl groups of (a).
2. The adhesive of claim 1, wherein x is 1 、x 2 、x 3 、x 4 Each independently is a number in the range of 0.1 to 0.45; a, a 1 、a 2 Each independently is a number in the range of 0.1-0.3.
3. The adhesive of claim 2, wherein x is 1 、x 2 、x 3 、x 4 Each independently is a number in the range of 0.15-0.4.
4. A binder according to any one of claims 1-3, wherein the halogen is selected from one of fluorine, chlorine, bromine; the amine group is selected from C 1 -C 6 Primary amine of C 1 -C 6 Alkyl-substituted secondary or tertiary aminesAn amine; the C is 1 -C 6 Is selected from methoxy or ethoxy; the C is 1 -C 6 The alkyl group of (a) is selected from methyl, ethyl, propyl, isopropyl, butyl or tert-butyl; the C is 6 -C 12 Is selected from phenyl, naphthyl or biphenyl; the C is 6 -C 12 Is selected from cyclohexyl or dicyclohexyl.
5. A binder according to any one of claims 1 to 3, wherein the mass ratio of carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer to polyamine compound is (10:1) - (1:5).
6. The binder of claim 5 wherein the mass ratio of carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer to polyamine is (5:1) - (1:2).
7. The binder of claim 4 wherein the mass ratio of carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer to polyamine is (10:1) - (1:5).
8. The binder of claim 7 wherein the mass ratio of carboxyl modified polyvinyl alcohol and/or carboxyl modified polyvinyl alcohol copolymer to polyamine is (5:1) - (1:2).
9. The binder of any one of claims 1-3 and 6-8 wherein the polyamine compound contains two or more amine groups.
10. The binder of claim 4 wherein the polyamine compound contains two or more amine groups.
11. The binder of claim 5 wherein the polyamine compound contains two or more amine groups.
12. The adhesive according to claim 9, wherein the polyamine-based compound contains at least one structural unit selected from the group consisting of a structure represented by formula (5), a structure represented by formula (6), a structure represented by formula (7), and a structure represented by formula (8);
wherein n is 1 、n 2 、n 3 、n 4 Each independently is an integer from 2 to 100000.
13. The adhesive according to claim 12, wherein the polyamine-based compound has a structure represented by the formula (5).
14. The adhesive according to claim 10 or 11, wherein the polyamine compound contains a structural unit selected from at least one of a structure represented by formula (5), a structure represented by formula (6), a structure represented by formula (7) and a structure represented by formula (8);
wherein n is 1 、n 2 、n 3 、n 4 Each independently is an integer from 2 to 100000.
15. The adhesive according to claim 14, wherein the polyamine-based compound has a structure represented by formula (5).
16. The binder of claim 9 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.1-0.3): (0.4-0.8): (0.1-0.3).
17. The binder of claim 16 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.15-0.25): (0.5-0.7): (0.15-0.25).
18. The binder of any one of claims 10-13 and 15 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.1-0.3): (0.4-0.8): (0.1-0.3).
19. The binder of claim 18 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.15-0.25): (0.5-0.7): (0.15-0.25).
20. The binder of claim 14 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.1-0.3): (0.4-0.8): (0.1-0.3).
21. The binder of claim 20 wherein, in the polyamine-based compound, tertiary amine: secondary amine: the molar ratio of the primary amine is (0.15-0.25): (0.5-0.7): (0.15-0.25).
22. A negative electrode comprising a negative electrode current collector and a negative electrode active material layer on a surface of the current collector, the negative electrode active material layer comprising a negative electrode active material and a binder, wherein the binder is the binder of any one of claims 1 to 21.
23. The anode according to claim 22, wherein the content of the binder in the anode active material layer is 5 to 40wt%.
24. A lithium ion battery comprising the negative electrode of claim 22 or 23.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013178962A (en) * | 2012-02-28 | 2013-09-09 | Sekisui Chem Co Ltd | Composition for lithium secondary battery electrode |
| CN105659419A (en) * | 2014-03-27 | 2016-06-08 | 积水化学工业株式会社 | Binder for power storage device electrode |
| CN108028387A (en) * | 2016-04-01 | 2018-05-11 | 积水化学工业株式会社 | Lithium secondary battery electrode composition |
| WO2019242318A1 (en) * | 2018-06-20 | 2019-12-26 | 深圳市贝特瑞新能源材料股份有限公司 | Waterborne binder, preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013178962A (en) * | 2012-02-28 | 2013-09-09 | Sekisui Chem Co Ltd | Composition for lithium secondary battery electrode |
| CN105659419A (en) * | 2014-03-27 | 2016-06-08 | 积水化学工业株式会社 | Binder for power storage device electrode |
| CN108028387A (en) * | 2016-04-01 | 2018-05-11 | 积水化学工业株式会社 | Lithium secondary battery electrode composition |
| WO2019242318A1 (en) * | 2018-06-20 | 2019-12-26 | 深圳市贝特瑞新能源材料股份有限公司 | Waterborne binder, preparation method therefor and use thereof |
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