CN117276543A - Binder for secondary battery, negative electrode slurry composition, negative electrode, and secondary battery - Google Patents
Binder for secondary battery, negative electrode slurry composition, negative electrode, and secondary battery Download PDFInfo
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- CN117276543A CN117276543A CN202310751526.2A CN202310751526A CN117276543A CN 117276543 A CN117276543 A CN 117276543A CN 202310751526 A CN202310751526 A CN 202310751526A CN 117276543 A CN117276543 A CN 117276543A
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- repeating unit
- secondary battery
- binder
- negative electrode
- cmc
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- 239000011230 binding agent Substances 0.000 title claims abstract description 43
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 23
- 239000001913 cellulose Substances 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 239000002562 thickening agent Substances 0.000 abstract description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 66
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 65
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 64
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 63
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000007864 aqueous solution Substances 0.000 description 38
- 241000872931 Myoporum sandwicense Species 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 125000003172 aldehyde group Chemical group 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001976 hemiacetal group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 lithium carboxylates Chemical class 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012710 chemistry, manufacturing and control Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a binder for a secondary battery, a negative electrode slurry composition, a negative electrode and a secondary battery, which comprise cellulose derivatives, and solve the problem of poor flexibility of the cellulose derivatives when the cellulose derivatives are used as dispersing agents, thickening agents and binders in the production process of the secondary battery by selectively breaking a C-C bond between C2 and C3 on a main chain ring structure of the cellulose derivatives.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a binder for a secondary battery, a negative electrode slurry composition, a negative electrode and a secondary battery.
Background
Secondary batteries, also called rechargeable batteries or secondary batteries, are batteries that can be used continuously by activating active materials by charging after the battery is discharged. The binder is an indispensable auxiliary material in the process of preparing the secondary battery, and a cellulose derivative such as carboxymethyl cellulose (CMC) is currently used as a binder in a large amount.
Taking CMC as an example, CMC has better dispersibility, thickening property and binding force when being used as a secondary battery binder, but is hard and brittle after film formation, has poorer flexibility and is unfavorable for the production and processing of secondary batteries.
Disclosure of Invention
The invention aims to provide a binder for a secondary battery, a negative electrode slurry composition, a negative electrode and a secondary battery, which are used for solving the problem that cellulose derivatives are poor in flexibility when used as a dispersing agent, a thickening agent and a binder in a secondary battery production process.
In order to achieve the above object, the present invention provides a binder for a secondary battery, comprising a cellulose derivative including a repeating unit a and a repeating unit B, the repeating unit a being,
the repeating unit B is a group of units,
wherein, in the repeating unit A and the repeating unit B, R is independently selected from one or more of-OH or a derivative thereof; in the repeating unit B, R 1 Independently selected from one or more of —cho-derived groups; when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
wherein when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
wherein when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
wherein in the repeating unit B, R 1 Independently selected from at least one of-OH, -COOH, -COONa and-COOLi.
Wherein in the repeating unit B, R 1 Independently selected from at least one of-COOH, -COONa and-COOLi.
Wherein R is independently selected from the group consisting of-OH, -OCH, in said repeating unit A and said repeating unit B 2 COOH、—OCH 2 COONa and-OCH 2 At least one of COOLi.
A secondary battery negative electrode slurry composition comprising the binder for secondary batteries.
A secondary battery negative electrode has an electrode composite layer made using the secondary battery negative electrode slurry composition.
A secondary battery has the secondary battery negative electrode.
The binder for the secondary battery is applied to a battery separator, or a lithium iron phosphate positive electrode, or a carbon-coated copper foil current collector.
The binder for the secondary battery, the negative electrode slurry composition, the negative electrode and the secondary battery provided by the invention have good flexibility, and the manufactured electrode pole piece has no obvious fracture after being subjected to flexibility test, so that the processing performance of the pole piece is obviously improved; and is used in a secondary battery, the first efficiency and cycle performance of the battery are not deteriorated. Solves the problem of poor flexibility of the cellulose derivative when used as a dispersing agent, a thickening agent and a binder in the production process of the secondary battery.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a photograph of a flexibility test of a battery negative electrode tab of example 7 of the present invention.
Fig. 2 is a photograph of the battery negative electrode tab of comparative example 1 tested for flexibility.
Detailed Description
The following detailed description of embodiments of the invention, examples of which are illustrated in the accompanying drawings and, by way of example, are intended to be illustrative, and not to be construed as limiting, of the invention.
The "binder for secondary batteries" according to the present invention is not to be construed as merely a binding action, but may be construed as a dispersing agent for secondary batteries, a thickening agent for secondary batteries, a suspending agent for secondary batteries, and the like.
Numerical ranges in this disclosure are understood to also specifically disclose each intermediate value between the upper and lower limits of the ranges. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The experimental methods used in the present invention are conventional methods unless otherwise specified.
The materials, reagents and the like used in the present invention can be synthesized by a method of purchase or known method unless otherwise specified.
The present invention provides a binder for a secondary battery, comprising a cellulose derivative comprising a repeating unit a and a repeating unit B: the repeating unit A is a group of the amino acid,
the repeating unit B is a group of units,
wherein, in the repeating unit A and the repeating unit B, R is independently selected from one or more of-OH or a derivative thereof; in the repeating unit B, R 1 Independently selected from one or more of —cho-derived groups; when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
in the repeating unit B, R 1 Independently selected from at least one of-OH, -COOH, -COONa and-COOLi.
In the repeating unit B, R 1 Independently selected from at least one of-COOH, -COONa and-COOLi.
In the repeating unit A and the repeating unit B, R is independently selected from-OH, -OCH 2 COOH、—OCH 2 COONa and-OCH 2 At least one of COOLi.
With the binder for secondary battery of the present embodiment, R in the repeating unit A and the repeating unit B mentioned above represents a hydroxyl group and/or a derivative thereof, it should be specifically noted that, in the embodiment of the present invention, R on the repeating unit A and the repeating unit B may independently represent different groups, and those skilled in the art know that R groups on cellulose represent-OH when not modified, and that-OH may be changed into a derivative functional group by etherification, esterification, grafting or the like in the prior art, for example, -OH is derived into-OCH 2 COOH、—OCH 3 、—OCH 2 CH 3 、—[OCH 2 CH(CH 3 )O] n CH 3 、—OCH 2 CH 2 OH、—ONO 2 、—OSO 3 Na, etc.; illustratively, in one embodiment, 3R groups in repeating unit A each represent-OH, -OCH 2 COONa and-OCH 2 COOLi, R in the repeating unit B represents-OCH 2 COOLi; in another embodiment, 3R groups in the repeating unit A each represent-OH, -OCH 2 CH 3 COONa、—OCH 2 OH, R in the repeating unit B represents-OSO 3 Na (Na); r in the above repeating unit B 1 Represents groups derived from aldehyde groups, it being noted that, in the examples of the invention, R on the repeating unit B 1 Can be independently represented as different groups, illustratively, aldehyde groups can be derivatized to carboxyl groups by oxidation, to hydroxyl groups by reduction, to both hydroxyl and carboxyl groups by disproportionation, and to other functional groups such as hemiacetals, illustratively, repeating a single in one embodimentR in element B 1 Represents hydroxy, R in the repeating unit B in another embodiment 1 Represents a functional group further derivatised by a hydroxyl group, in the same way reference is made to the derivatisation of the R group, in other embodiments R in the repeating unit B 1 Represents carboxyl groups, carboxylic acid salts, for example sodium or lithium carboxylates.
The binder for the secondary battery provided by the invention can be used for remarkably solving the problem that the existing cellulose derivative is poor in flexibility when being used as a dispersing agent, a thickening agent and a binder in the preparation and production process of the secondary battery. At present, cellulose derivatives used in the preparation and production processes of secondary batteries mainly comprise carboxymethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose and the like, and the cellulose derivatives have the problems of strong rigidity and poor flexibility, so that slurry coating processing is difficult, and the prepared electrode plate is easy to crack. In the prior art, in order to solve the problem, a cellulose derivative and other materials with better flexibility are usually used in a matched manner, for example, CMC and SBR are mixed (styrene butadiene rubber), and SBR has certain flexibility compared with CMC, but still cannot meet the production process requirements of the lithium battery negative electrode plate. In order to improve the brittleness of the pole piece, most manufacturers add small-molecule plasticizers into the formulation, but the addition of the plasticizers consumes part of lithium, resulting in a decrease in battery capacity. In addition, there are also some related arts for modifying cellulose derivatives in order to improve flexibility of the cellulose derivatives. For example, the brittleness of carboxymethyl cellulose is improved by introducing a non-ionic group with weak polarity on the cellulose side chain, partially substituting a strong polar group such as hydroxyl group and carboxyl ether. This way, by reducing the hydrogen bonding between molecules caused by polar groups, the relative movement between molecules is made easier, thus rendering the whole softer; however, the reason why carboxymethyl cellulose plays a role in the adhesion of secondary batteries is that it has a large number of strong polar groups on its side chains, and decreasing the proportion of the strong polar groups causes the adhesion to decrease, which is manifested as pole piece powder falling in secondary battery applications. And the flexibility of the carboxymethyl cellulose is changed by adjusting the distribution proportion of the substituted positions of the carboxymethyl groups, but the cellulose has only one more methylene group than C6 and C2 and C3, the advantage of long chain is not obvious, and the flexibility of the carboxymethyl cellulose is limited by the limitation of the whole substitution degree. For example, by breaking the-C-O-C-bond in CMC with a strong acid, grafting a flexible material, the flexibility of the rigid cyclic segment is improved; C-O-C-is a bond between the repeating units of the CMC main chain, and after the CMC main chain is disconnected, the CMC polymerization degree is inevitably greatly reduced, the viscosity is greatly reduced, and the suspension property and the thickening property are greatly reduced when the CMC is used in secondary battery slurry. Compared with the prior art, the cellulose derivative provided by the embodiment of the invention selectively breaks the-C bond between C2 and C3 on the main chain annular structure, so that the rigid annular structure which cannot rotate originally is changed into a flexible chain structure, and the flexibility of the cellulose derivative is obviously improved.
In the examples of the present invention, when the molar amount of the repeating unit A is represented by a and the molar amount of the repeating unit B is represented by B,in some embodiments, the relationship of a and b satisfies +.>Or->Or->In some preferred embodiments, the relation of a and b also satisfies +.>Or alternativelyOr->
The embodiment of the invention also provides a secondary battery negative electrode slurry composition containing the binder for the secondary battery, a negative electrode with an electrode composite layer formed by the secondary battery negative electrode slurry composition, and a secondary battery with the negative electrode. The secondary battery provided by the embodiment of the invention has lower direct current internal resistance and better capacity retention rate after circulation.
While the present invention has been illustrated in the following detailed description in order to provide a thorough understanding of the present invention, the present invention may be embodied in other forms than those described herein, and persons skilled in the art may readily devise numerous specific details that do not depart from the spirit of the invention and therefore the invention is not limited to the specific embodiments disclosed below.
Example 1:
< configuration of reactant >
An aqueous CMC solution of 0.1mol/L was prepared based on the number of moles of anhydroglucose units of sodium carboxymethylcellulose (CMC, substitution degree 0.8 to 0.9).
NaIO is carried out 4 Dissolving in water under light-shielding environment, and preparing NaIO of 0.1mol// L 4 An aqueous solution.
NaBH4 was dissolved in water at room temperature to prepare a 0.1mol/L aqueous NaBH4 solution.
< reaction Process >
The first stage: placing the above CMC aqueous solution into a light-proof reaction container, heating to 40deg.C, maintaining the temperature, and mixing with NaIO of the same volume as CMC aqueous solution 4 Slowly dropping the aqueous solution into the reaction vessel (CMC and NaIO) 4 The molar ratio of (2) is 1: 1) The mechanical stirring speed was adjusted to 500rpm, and 1mol/L H was used 2 SO 4 The reaction was started after the pH of the reaction environment was adjusted to 4, and after the reaction time had been reached, the reaction pH was adjusted to 7 with 1mol/L NaOH.
And a second stage: slowly adding NaBH4 water solution (CMC, naIO) with the same volume as the CMC water solution in the first stage 4 And NaBH4 in a molar ratio of 1:1: 1) The stirring speed is controlled at 300rpm, the temperature of the reaction system is reduced to about 5 ℃,reacting for 2H with 1mol/L H 2 SO 4 The pH of the solution was adjusted to 7 to achieve the end of the reaction.
< separation and purification >
After the reaction is completed, slowly pouring the mixed liquid after the reaction into a large amount of frozen methanol to precipitate out, filtering, and drying at room temperature to obtain a solid product, namely the binder for the secondary battery provided by the embodiment of the invention.
Example 2:
< configuration of reactant >
An aqueous CMC solution of 0.1mol/L was prepared based on the number of moles of anhydroglucose units of sodium carboxymethylcellulose (CMC, substitution degree 0.8 to 0.9).
NaIO is carried out 4 Dissolving in water under light-shielding environment, and preparing NaIO of 0.1mol// L 4 An aqueous solution.
NaClO is processed by 2 Dissolving in water at room temperature to obtain NaClO of 0.1mol/L 2 Aqueous solution
< reaction Process >
The first stage: placing the above CMC aqueous solution into a light-proof reaction container, heating to 40deg.C, maintaining the temperature, and mixing with NaIO of the same volume as CMC aqueous solution 4 Slowly dropping the aqueous solution into the reaction vessel (CMC and NaIO) 4 The molar ratio of (2) is 1: 1) The mechanical stirring speed was adjusted to 500rpm, and 1mol/L H was used 2 SO 4 The reaction was started after the pH of the reaction environment was adjusted to 4, and after the reaction time had been reached, the reaction pH was adjusted to 7 with 1mol/L NaOH.
And a second stage: slowly adding NaClO with the same volume as the CMC aqueous solution in the first stage 2 Aqueous solutions (CMC, naIO) 4 And NaClO 2 The molar ratio of (2) is 1:1: 1) The stirring speed is controlled at 300rpm, the temperature of the reaction system is reduced to about 5 ℃ for 2H, and 1mol/L H is used 2 SO 4 The pH of the solution was adjusted to 7 to achieve the end of the reaction.
< separation and purification >
After the reaction is completed, the mixed liquid after the reaction is dripped into a large amount of absolute ethyl alcohol, flocculent products are observed to be separated out, the precipitate is filtered, a filter cake is collected, deionized water and absolute ethyl alcohol are used for alternately washing the filter cake, and the washed filter cake is dried at the constant temperature of 60 ℃ for 12 hours, so that a solid product is obtained, namely the binder for the secondary battery provided by the embodiment of the invention.
Example 3:
the difference from example 2 is only that the binder for secondary battery provided in the example of the present invention was obtained by directly separating and purifying after the first stage reaction.
Example 4: the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.8; the volume of CMC aqueous solution V participating in the reaction is 0.8V NaIO 4 The aqueous solution was mixed with 0.2V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 5:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.6; the volume of CMC aqueous solution V participating in the reaction is 0.6V NaIO 4 The aqueous solution was mixed with 0.4V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 6:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.5; the volume of CMC aqueous solution V participating in the reaction is 0.5V NaIO 4 The aqueous solution was mixed with 0.5V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 7:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.4; the volume of CMC aqueous solution V participating in the reaction is 0.4V NaIO 4 The aqueous solution was mixed with 0.6V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 8:
the difference from example 7 is only that the binder for secondary battery provided in the example of the present invention was obtained by directly separating and purifying after the first-stage reaction.
Example 9: the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.3The method comprises the steps of carrying out a first treatment on the surface of the The volume V of CMC aqueous solution which participates in the reaction is 0.3V NaIO 4 The aqueous solution was mixed with 0.7V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 10:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.2; the volume of CMC aqueous solution V participating in the reaction is 0.2V NaIO 4 The aqueous solution was mixed with 0.8V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 11:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.15; the volume V of CMC aqueous solution which participates in the reaction is 0.15V NaIO 4 The aqueous solution was mixed with 0.5V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 12:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.1; the volume of CMC aqueous solution V participating in the reaction is 0.1V NaIO 4 The aqueous solution was mixed with 0.9V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 13:
the only difference from example 1 is the first reaction stage CMC and NaIO 4 The molar ratio of (2) is 1:0.05; the volume of CMC aqueous solution V participating in the reaction is 0.05V NaIO 4 The aqueous solution was mixed with 0.95V deionized water and slowly added dropwise to the CMC aqueous solution.
Example 14: the difference from example 2 is only that the sodium carboxymethylcellulose used in the first reaction stage has a degree of substitution of 0.3 to 0.4.
Comparative example 1: CMC without modification (degree of substitution 0.8-0.9).
< b/a+b measurement >
The number of moles of the repeating unit A is represented by a, the number of moles of the repeating unit B is represented by B, and the value of B/a+b is measured. Taking the solution obtained after the first-stage reaction of examples 1-14, and measuring the aldehyde group content in the solution by adopting a hydroxylamine hydrochloride method, wherein the measurement mode is as follows: wang Qinmei, liao Yangong, teng Wei, et al, hydroxylamine hydrochloride-potentiometric titration to determine the aldehyde concentration [ J ] on oxidized sodium alginate analytical laboratories, 2008, 27 (S1): 83-86.
Since the relative molecular mass of the reacted solid product compared to the repeating unit structure of the reactant CMC is unchanged, b=mole aldehyde groups/2 measured.
TABLE 1 comparison of reaction conditions for examples 1-14 and comparative example 1
< Performance test >
Cell fabrication
And preparing the negative electrode plate according to a conventional process. The cathode active material, the conductive agent, the binder and the SBR are prepared from 96.3% by mass: 0.7%:1.2%:1.8% of the negative electrode slurry; the negative electrode active material was artificial graphite, the conductive agent was conductive carbon black, the binder was the solid products of examples 1 to 14, and unmodified CMC (substitution degree 0.8 to 0.9) was used as the binder in comparative example 1. Single-sided surface density of the prepared negative electrode plate: 14-15 mg/cm2, thickness of the pole piece: 150-160 um, cutting the size of the pole piece: 5 x 5cm.
And preparing the positive plate according to a conventional process. Positive electrode active material, conductive agent and binder 97% by mass: 2%:1% is configured as positive electrode slurry; the positive electrode active material is nickel-cobalt-manganese ternary material (523 proportion: nickel 50%, cobalt 20% and manganese 30%), the conductive agent is conductive carbon super-p, and the binder is PVDF (Suwei 5130).
The diaphragm adopts 7um basal membrane, single-sided 3um ceramic and 1um glue-coated diaphragms on both sides; the electrolyte adopts a conventional formula, 1mol/L LiPF6 lithium salt and a solvent EC (ethylene carbonate): PC (propylene carbonate): the mass ratio of DEC (diethyl carbonate) is 3:1:3, a step of; the additive VC (vinylene carbonate) accounts for 0.3% of the electrolyte mass ratio, and PS (1, 3-propane sultone) accounts for 0.1% of the electrolyte mass ratio.
The battery structure is as follows: and assembling small soft-package batteries with two sides provided with lugs according to the material system.
Performance testing
And (3) placing the negative pole piece on a cylinder with the diameter of 8mm for bending, and observing the fracture condition of the pole piece coating to evaluate the flexibility of the pole piece.
The first efficiency and the charge-discharge cycle performance of the battery cell are tested according to national standard GB/T31486-2015. The test results are shown in table 2:
table 2 electrochemical performance test results table
As can be seen from the test results of Table 1, examples 1 to 13 of the present invention were modified with CMC having a substitution degree of 0.8 to 0.9, the ratio of b/(a+b) was measured to be 0.63 at the maximum, and example 14 was modified with CMC having a substitution degree of 0.3 to 0.4, and the ratio of b/(a+b) was measured to be 0.83. Fig. 1 exemplarily provides a picture of the results of the battery negative electrode tab flexibility test of example 7 without breakage, and fig. 2 shows the occurrence of significant breakage during the negative electrode tab flexibility test of the battery of comparative example 1. The modified CMCs provided in examples 1-14 of the present invention all had a significant improvement in flexibility over the unmodified CMC in comparative example 1, and the higher the degree of improvement in CMC flexibility with increasing B/(a+b), but in examples 3 and 8, the flexibility was instead decreased with increasing B/(a+b), presumably because of R in repeating units B of examples 3 and 8 1 Are all aldehyde groups, and as the concentration of aldehyde groups increases, hemiacetals form between aldehyde groups, limiting molecular movement, and thus exhibiting lower flexibility of the material than b/(a+b) at the appropriate level. In addition, instead of indirectly measuring the value of B by measuring the aldehyde content by the hydroxylamine hydrochloride method, in other specific embodiments, the measurement may be performed by other means such as nuclear magnetism, infrared spectroscopy, etc., for example, by measuring the main chain structure of the repeating unit B by nuclear magnetism to determine the ratio of B/(a+b).
Second, as can be seen from the test results of table 2, the first efficiencies of the other example batteries are substantially equal to those of comparative example 1 except for examples 3 and 8; the first significant reduction in efficiency of example 3 and example 8 compared to comparative example 1 may be affected by the aldehyde groups on the modified CMC.
Finally, the capacity retention after 1500 weeks of cycling for most of the cells of example in table 2 was substantially the same as that of comparative example 1, indicating that the binder provided by this example was modified without a decrease in adhesion; the battery capacity retention rates of examples 2 and 14 are significantly better than comparative example 1, presumably because the binders provided in examples 3 and 14 have more carboxyl groups or carboxylate groups, which are strongly polar functional groups, providing stronger adhesion; while the battery capacity retention rates of example 3 and example 8 were inferior to those of comparative example 1, it is assumed that they are affected by aldehyde groups.
When the specific description is needed, the application of the cellulose derivative in the secondary battery can be used as a binder, a dispersing agent and a thickening agent of a battery negative electrode, and can also be used as a binder, a dispersing agent and a thickening agent of a battery separator coating slurry, a lithium iron phosphate positive electrode slurry and a carbon coating slurry of a battery copper foil current collector, and the application situations are basically consistent with the performance requirements of the binder.
The foregoing disclosure is only illustrative of one or more preferred embodiments of the present application and is not intended to limit the scope of the claims hereof, as it is to be understood by those skilled in the art that all or part of the process of implementing the described embodiment may be practiced otherwise than as specifically described and illustrated by the appended claims.
Claims (10)
1. A binder for a secondary battery comprising a cellulose derivative, characterized in that:
the cellulose derivative comprises a repeating unit A and a repeating unit B, wherein the repeating unit A is,
the repeating unit B is a group of units,
wherein, in the repeating unit A and the repeating unit B, R is independently selected from one or more of-OH or a derivative thereof; in the repeating unit B, R 1 Independently selected from one or more of —cho-derived groups; when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
2. the binder for a secondary battery according to claim 1, wherein:
when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
3. the binder for a secondary battery according to claim 1, wherein:
when the molar amount of the repeating unit a is represented by a and the molar amount of the repeating unit B is represented by B, the relationship is satisfied:
4. the binder for a secondary battery according to claim 1, wherein:
in the repeating unit B, R 1 Independently selected from at least one of-OH, -COOH, -COONa and-COOLi.
5. The binder for a secondary battery according to claim 1, wherein:
in the repeating unit B, R 1 Independently selected from at least one of-COOH, -COONa and-COOLi.
6. The binder for a secondary battery according to claim 1, wherein:
in the repeating unit A and the repeating unit B, R is independently selected from-OH, -OCH 2 COOH、—OCH 2 COONa and-OCH 2 At least one of COOLi.
7. A secondary battery negative electrode slurry composition characterized in that: a binder for a secondary battery according to any one of claims 1 to 6.
8. A secondary battery negative electrode, characterized in that: an electrode composite layer comprising the secondary battery negative electrode slurry composition according to claim 7.
9. A secondary battery characterized in that: a secondary battery negative electrode having the secondary battery negative electrode of claim 8.
10. The use of the binder for secondary batteries according to any one of claims 1 to 6 in a battery separator, or a lithium iron phosphate positive electrode, or a carbon coated copper foil current collector.
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| PCT/CN2024/108368 WO2025002470A1 (en) | 2023-06-25 | 2024-07-30 | Binder for secondary battery, negative electrode slurry composition, negative electrode and secondary battery |
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| KR102038070B1 (en) * | 2016-07-12 | 2019-10-30 | 주식회사 엘지화학 | Binder for secondary battery electrode, composition comprising the same and secondary battery using the same |
| CN106531963B (en) * | 2016-09-21 | 2019-12-17 | 珠海光宇电池有限公司 | Lithium ion battery cathode slurry and lithium ion battery |
| KR20200123781A (en) * | 2018-02-27 | 2020-10-30 | 니폰 제온 가부시키가이샤 | Slurry composition for lithium ion secondary battery and electrode for lithium ion secondary battery |
| CN111384369A (en) * | 2018-12-29 | 2020-07-07 | 北方奥钛纳米技术有限公司 | Negative electrode material and preparation method thereof, manufacturing method of negative electrode piece and lithium ion battery |
| EP3872906B1 (en) * | 2019-12-24 | 2023-08-23 | Resonac Corporation | Nonaqueous secondary battery electrode, electrode slurry, and nonaqueous secondary battery |
| US12046756B2 (en) * | 2020-10-30 | 2024-07-23 | Electronics And Telecommunications Research Institute | Cellulose derivative composition for secondary battery binder and method of preparing composition for secondary battery electrode comprising the same |
| CN115832311A (en) * | 2022-12-29 | 2023-03-21 | 重庆硕盈峰新能源科技有限公司 | Lithium ion battery negative electrode binder, slurry, negative electrode plate and lithium battery |
| CN117276543A (en) * | 2023-06-25 | 2023-12-22 | 重庆硕盈峰新能源科技有限公司 | Binder for secondary battery, negative electrode slurry composition, negative electrode, and secondary battery |
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