CN117317233B - Positive electrode slurry, preparation method and application - Google Patents
Positive electrode slurry, preparation method and application Download PDFInfo
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- CN117317233B CN117317233B CN202311597644.9A CN202311597644A CN117317233B CN 117317233 B CN117317233 B CN 117317233B CN 202311597644 A CN202311597644 A CN 202311597644A CN 117317233 B CN117317233 B CN 117317233B
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 109
- 239000011230 binding agent Substances 0.000 claims abstract description 124
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 229920000447 polyanionic polymer Polymers 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 239000011888 foil Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- -1 sodium nickel iron manganate Chemical compound 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M2004/028—Positive 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)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode slurry, a preparation method and application thereof, wherein the positive electrode slurry comprises a combination of a sodium ion battery positive electrode material, a binder, a conductive agent and a nonaqueous solvent; the binder comprises a compound with a structure shown in a formula I; in the formula I, p is more than 0, m is more than 0, n is more than or equal to 0 and less than or equal to 20%, and p+m+n=100%. According to the invention, the compound with the structure shown in the formula I is introduced into the positive electrode slurry as the binder, so that the slurry gel phenomenon caused by long-term storage of the positive electrode slurry can be effectively improved or eliminated, the storage time of the positive electrode slurry is prolonged, and the viscosity stability of the positive electrode slurry is improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to positive electrode slurry, a preparation method and application thereof.
Background
Compared with a lithium ion battery, the sodium ion battery is characterized by wide resources, low price, high safety and the like, the process route of the sodium ion battery is consistent with that of the lithium ion battery, and the manufacturing process and equipment can adopt the latter, and an oily polyvinylidene fluoride (PVDF) and N-methylpyrrolidone solvent system is generally adopted. However, when PVDF encounters high alkalinity, HF is removed to generate double bonds, and crosslinking occurs, so that the viscosity of the slurry increases, and when the positive electrode in the battery undergoes oxidation reaction, the PVDF is easily oxidized and then broken in molecular chains, so that PVDF fails, and the coating is peeled off, so that the internal resistance and capacity of the battery increase. The alkaline of the positive electrode material of the sodium ion battery is higher, the residual alkaline is even much larger than that of the ternary material of the nickel positive electrode, the slurry prepared by mixing the conventional PVDF binder and the positive electrode material of the sodium ion battery is left standing for 2 h to form gel, and the viscosity is greatly increased to cause the fluctuation of the coating thickness of the positive electrode or incapability of coating.
CN116885194a discloses a sodium ion positive electrode slurry, a preparation method thereof and a sodium ion battery containing the sodium ion positive electrode slurry, wherein the sodium ion positive electrode slurry comprises the following raw materials in parts by weight: 80-100 parts of sodium ion active material, 0.02-0.1 part of single-walled carbon nanotube, 0.02-0.1 part of graphite, 2-5 parts of binder, 0.1-0.3 part of dispersing agent, 50-60 parts of solvent and 3-5 parts of regulator; the regulator is citric acid, ascorbic acid, hexahydrophthalic anhydride and ethyl acetate. According to the technical scheme, citric acid, ascorbic acid and ethyl acetate are used for compounding, alkaline substances in a sodium ion positive electrode slurry system are neutralized, the pH value of the sodium ion positive electrode slurry is reduced, the phenomenon of gel generation is reduced, and the uniformity and fluidity of the sodium ion positive electrode slurry are improved.
CN114497521a discloses a positive electrode slurry of a sodium ion battery and a preparation method thereof, wherein the positive electrode slurry of the sodium ion battery comprises the following raw material components: 46% -48% of positive electrode active material, 1.3% -1.8% of binder, 0.5% -1% of conductive agent, 0.1% -0.8% of inhibitor, 0.1% -0.5% of dispersing agent and 48% -52% of solvent. The inhibitor is oxalic acid or maleic anhydride. According to the technical scheme, the slurry fluidity is improved through the combined action of the inhibitor and the dispersing agent, and the gelation of the high-alkalinity slurry and the agglomeration of small-particle-size particles are inhibited.
In the prior art, acidic substances such as citric acid and oxalic acid are added into the sodium ion battery positive electrode slurry to neutralize alkaline substances in a sodium ion positive electrode slurry system, so that the slurry gel phenomenon is solved, the sodium ion positive electrode material is uniformly stirred in the pulping process and does not gel, particle scratches are avoided in the slurry coating process, the addition amount of the acidic substances is strictly controlled, the substances with stronger acidity are easy to damage the structure of the materials, and the performance of the prepared sodium ion battery is greatly influenced.
Therefore, how to provide a positive electrode slurry with good anti-gel effect, so as to increase the storage time of the positive electrode slurry, has become a technical problem to be solved in the present day.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide positive electrode slurry, and a preparation method and application thereof. According to the invention, the compound with the structure shown in the formula I is introduced into the positive electrode slurry as the binder, so that the slurry gel phenomenon caused by long-term storage of the positive electrode slurry can be effectively improved or eliminated, the storage time of the positive electrode slurry is prolonged, and the viscosity stability of the positive electrode slurry is improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode slurry comprising a combination of a sodium ion battery positive electrode material, a binder, a conductive agent, and a nonaqueous solvent;
the binder comprises a compound with a structure shown in a formula I;
i is a kind of
In the formula I, p is more than 0, m is more than 0, n is more than or equal to 0 and less than or equal to 20%, and p+m+n=100%.
In the invention, p is the molar ratio of a structural unit formula II in the compound with the structure shown in the formula I, m is the molar ratio of a structural unit formula III in the compound with the structure shown in the formula I, and n is the molar ratio of a structural unit formula IV in the compound with the structure shown in the formula I.
、/>、/>。
In the invention, the structural unit-CN in the structural unit formula III and the structural unit-F in the structural unit formula IV in the compound with the structure shown in the formula I have larger electronegativity, can generate an electron induction effect with the foil, increase the cohesiveness with the foil, can provide flexibility, and simultaneously have smaller occupied ratio of the structural unit formula II and the structural unit formula IV, are not easy to cause F elimination reaction under alkaline conditions, and can improve the gel problem of alkaline slurry. Therefore, the adhesive has stronger flexibility and cohesiveness to foil, and the compound with the structure shown in the formula I is introduced into the positive electrode slurry as the adhesive, so that the slurry gel phenomenon caused by long-term storage of the positive electrode slurry can be effectively improved or eliminated, the storage time of the positive electrode slurry is prolonged, and the viscosity stability of the positive electrode slurry is improved. The surface density of the coating formed after the positive electrode slurry is coated is more stable, and the prepared positive electrode plate has good consistency, so that the consistency of sodium ion battery products is improved. The positive electrode plate prepared from the positive electrode slurry has excellent flexibility and excellent peel strength.
Preferably, the weight average molecular weight of the binder is 30-100 tens of thousands, for example 35-40, 45-50, 55-60, 65-70, 75-80, 85-90 or 95-tens of thousands, etc.
Preferably, the ratio of m to p is 0.2-0.8:1, e.g., 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, or 0.75:1, etc.
In the invention, if the ratio of m to p is too large, the flexibility of the positive pole piece prepared by adopting the positive pole slurry is poor, and the positive pole piece is easy to crack after winding; if the ratio of m to p is too small, the adhesion of the coating layer formed by the positive electrode slurry to the foil becomes small.
Preferably, the sodium ion battery positive electrode material comprises any one or a combination of at least two of layered transition metal oxide, prussian blue positive electrode material or polyanion compound.
Preferably, the layered transition metal oxide has the formula NaM x O y Wherein M is selected from one or a combination of at least two of iron, copper, nickel, cobalt or manganese, x is more than or equal to 0.8 and less than or equal to 1.5, y is more than or equal to 1.5 and less than or equal to 2.5, and the values of x and y meet the charge balance of a chemical formula.
The x may be 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, etc.
The y may be 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, etc.
Preferably, the polyanion compound has a structural formula of Na a M' b (XO 4 ) c Y d Wherein M' is any one or a combination of at least two of Fe, mn, V, cr, ti, ni or Co, X is Si and/or P, Y is F and/or P 2 O 7 ，0<a<5.0，0<b<4.0，0<c<4.0，0<d<4.0。
The a may be 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or the like.
The b may be 0.2, 0.4, 0.8, 1.2, 1.6, 2.0, 2.4, 2.8, 3.2, 3.6, 3.8, or the like.
The c may be 0.2, 0.4, 0.8, 1.2, 1.6, 2.0, 2.4, 2.8, 3.2, 3.6, 3.8, or the like.
The d may be 0.2, 0.4, 0.8, 1.2, 1.6, 2.0, 2.4, 2.8, 3.2, 3.6, 3.8, or the like.
Preferably, the conductive agent includes any one or a combination of at least two of carbon nanotubes, carbon black or conductive carbon black SP.
Preferably, the nonaqueous solvent includes any one or a combination of at least two of N-methylpyrrolidone (NMP), dimethylacetamide (DMAC) or Dimethylsulfoxide (DMSO).
Preferably, the positive electrode slurry comprises the following components in parts by weight: 69-75 parts (e.g., 69.5 parts, 70 parts, 70.5 parts, 71 parts, 71.5 parts, 72 parts, 72.5 parts, 73 parts, 73.5 parts, 74 parts, or 74.5 parts, etc.), 0.5-4 parts (e.g., 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 3.8 parts, etc.), 0.1-4 parts (e.g., 0.5 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 3.8 parts, etc.), and 20-28 parts (e.g., 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, or 27 parts, etc.) of a non-aqueous solvent.
In the invention, the weight part of the binder is 0.5-4 parts, if the weight part of the binder is too large, the proportion of the sodium ion battery anode material is reduced, the battery capacity is reduced, and the coverage area of the binder on the sodium ion battery anode material is increased, so that the sodium ion transmission is not facilitated; if the weight portion of the binder is too small, the positive electrode coating formed by the positive electrode slurry is easy to fall off, and the problem of material falling occurs.
Preferably, the positive electrode slurry has a viscosity change rate of 4. 4 h at 25 ℃ of 20% or less, for example 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, 17% or 19%, etc.
In a second aspect, the present invention provides a method for preparing the positive electrode slurry according to the first aspect, the method comprising the steps of: and mixing the sodium ion battery anode material, the binder, the conductive agent and the nonaqueous solvent to obtain the anode slurry.
In a third aspect, the invention provides a positive electrode plate, which comprises a current collector and a coating layer covered on the current collector, wherein the coating layer is prepared from the positive electrode slurry in the first aspect.
In a fourth aspect, the present invention provides a sodium ion battery comprising a positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the binder with the structure shown in the formula I is introduced into the positive electrode slurry, so that the slurry gel phenomenon caused by long-term storage of the positive electrode slurry can be effectively improved or eliminated, the storage time of the positive electrode slurry is prolonged, and the stability of the viscosity of the positive electrode slurry is improved. The adhesive with the structure shown in the formula I has stronger toughness and cohesiveness to foil, and the positive electrode plate prepared from the positive electrode slurry has excellent flexibility and excellent peel strength. The positive electrode plate prepared from the positive electrode slurry has good consistency, so that the consistency of sodium ion battery products is improved. The positive electrode slurry is not gelled after being placed at 25 ℃ for 6 hours, the viscosity change rate of the positive electrode slurry is 3.42% -26.99% after being placed at 25 ℃ for 4 hours, and the viscosity change rate of the positive electrode slurry is 3.42% -19.47% after being placed at 25 ℃ for 4 hours under the preferential condition, so that the positive electrode plate is complete in flexibility test and has no cracks.
Drawings
FIG. 1 is an infrared spectrum of binder A provided in preparation example 1;
fig. 2 is a scanning electron microscope image of a coating layer formed by the positive electrode slurry in the positive electrode sheet provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
The preparation example provides an adhesive, specifically an adhesive A, and the preparation method comprises the following steps:
under the condition of no water and no oxygen, 80 mL toluene and 5.586 g acrylonitrile are added into a 250 mL reactor, 12 mg azodiisoheptonitrile is added, 10g butadiene and 0.962g vinylidene fluoride are slowly introduced into the reactor under the stirring state, the reaction system is reacted at 70 ℃ for 24 h, after the reaction is finished, methanol is used for quenching and washing to prepare gel, butanone is used for dissolving the primary product of the gel to prepare glue solution, and 0.002g Rh (PPh) is added into a high-pressure reactor 3 ) 3 Cl is used as a catalyst, hydrogen is replaced for 3 times, excessive hydrogen is slowly introduced, reaction is carried out under the pressure of 8 Mpa at 140 ℃, 4 h is carried out, cooling is carried out, ethanol gel is used, a condensate is obtained, and the condensate is dried under the condition of 50 ℃ for 10 h, so that the binder A is obtained.
The adhesive A has a structure shown in the following formula I-1.
Formula I-1
In the formula I-1, n=5%, and m is p=0.6:1;
the weight average molecular weight of the binder A was 50 ten thousand.
Preparation example 2
The preparation example provides an adhesive, specifically an adhesive B, and the preparation method comprises the following steps:
under anhydrous and anaerobic conditions, to 250 mLAdding 80 mL toluene, 5.786g acrylonitrile, adding 16 mg azodiisoheptonitrile, slowly introducing 10g butadiene and 0.962g vinylidene fluoride under stirring, reacting at 70deg.C for 30 h, quenching with methanol, washing to obtain gel, dissolving the gel with butanone to obtain a primary product, adding into a high pressure reactor, adding 0.002g Rh (PPh 3 ) 3 Cl is used as a catalyst, hydrogen is replaced for 3 times, excessive hydrogen is slowly introduced, reaction is carried out under the pressure of 8 Mpa at 140 ℃, 4 h is carried out, cooling is carried out, ethanol gel is used, a condensate is obtained, and the condensate is dried under the condition of 50 ℃ for 10 h, so that the binder B is obtained.
The adhesive B has a structure shown in a formula I-2.
Formula I-2
In the formula I-2, n=5%, and m is p=0.6:1;
the weight average molecular weight of the binder B was 100 ten thousand.
Preparation example 3
The preparation example provides a binder, specifically a binder C, and the preparation method is as follows:
under the anhydrous and anaerobic condition, 80 mL toluene, 5.786g acrylonitrile and 10 mg azodiisoheptonitrile are added into a 250 mL reactor, 10g butadiene and 0.962g vinylidene fluoride are slowly introduced into the reactor under the stirring state, the reaction system is reacted at 70 ℃ for 20 h, after the reaction is finished, methanol is used for quenching and washing, gel is prepared, the gel is dissolved into preliminary product by butanone, a glue solution is prepared, the glue solution is put into a high-pressure reaction kettle, and 0.002g Rh (PPh 3 ) 3 Cl is used as a catalyst, hydrogen is replaced for 3 times, excessive hydrogen is slowly introduced, reaction is carried out at 140 ℃ and 8 Mpa pressure for 4 h, cooling is carried out, ethanol gel is used for obtaining condensate, and the condensate is dried at 50 ℃ for 10 h, so that the binder C is obtained.
The adhesive C has a structure shown in the following formula I-3.
Formula I-3
In the formula I-3, n=5%, and m is p=0.6:1;
the weight average molecular weight of the binder C is 30 ten thousand.
Preparation example 4
The present preparation example provides a binder, specifically binder D, which differs from preparation example 1 in that vinylidene fluoride was not introduced in the preparation method, and the other is the same as in preparation example 1.
The adhesive D has a structure shown in the following formula I-4.
Formula I-4
In the formula I-4, n=0%, and m is p=0.6:1;
the weight average molecular weight of the binder D was 50 ten thousand.
Preparation example 5
The present preparation example provides a binder, specifically a binder E, which is different from preparation example 1 in that the mass of vinylidene fluoride introduced by the preparation method is adjusted to 2.03 and g, and the other is the same as preparation example 1.
The adhesive E has a structure shown in the following formula I-5.
Formula I-5
In the formula I-5, n=10%, and m is p=0.6:1;
the weight average molecular weight of the binder E was 50 ten thousand.
Preparation example 6
The present preparation example provides a binder, specifically binder F, which is different from preparation example 1 in that the mass of vinylidene fluoride introduced by the preparation method is adjusted to 3.23g, and the other is the same as in preparation example 1.
The adhesive F has a structure shown in the following formula I-6.
Formula I-6
In the formula I-6, n=15%, and m is p=0.6:1;
the weight average molecular weight of the binder F was 50 ten thousand.
Preparation example 7
The present preparation example provides a binder, specifically binder G, which is different from preparation example 1 in that the mass of vinylidene fluoride introduced by the preparation method is adjusted to 4.57G, and the other is the same as in preparation example 1.
The adhesive G has a structure shown in the following formula I-7.
Formula I-7
In the formula I-7, n=20%, and m is p=0.6:1;
the weight average molecular weight of the binder G was 50 ten thousand.
Preparation example 8
The present preparation example provides a binder, specifically binder H, which is different from preparation example 1 in that the mass of azobisisoheptonitrile was adjusted to 8 mg, the reaction time at 70 ℃ was adjusted to 18H, and the other is the same as preparation example 1.
The adhesive H has a structure shown in the following formula I-8.
Formula I-8
In the formula I-8, n=5%, and m is p=0.6:1;
the weight average molecular weight of the binder H was 25 ten thousand.
Preparation example 9
The present preparation example provides a binder, specifically binder I, which is different from preparation example 1 in that the mass of azobisisoheptonitrile was adjusted to 20 mg, the reaction time at 70 ℃ was adjusted to 36 h, and the other is the same as preparation example 1.
The adhesive I has a structure shown in the following formula I-9.
Formula I-9
In the formula I-9, n=5%, and m is p=0.6:1;
the weight average molecular weight of the binder I was 110 ten thousand.
Preparation example 10
The present preparation example provides a binder, specifically binder K, which is different from preparation example 1 in that the mass of acrylonitrile in the preparation method is adjusted to 1.93g, the mass of butadiene is adjusted to 10g, and the other is the same as preparation example 1.
The adhesive K has a structure shown in the following formula I-10.
Formula I-10
In the formula I-10, n=5%, m is p=0.2:1;
the weight average molecular weight of the binder K was 50 ten thousand.
PREPARATION EXAMPLE 11
The present preparation example provides a binder, specifically binder L, which is different from preparation example 1 in that the mass of acrylonitrile in the preparation method was adjusted to 7.72g, the mass of butadiene was adjusted to 10g, and the other is the same as preparation example 1.
The adhesive L has a structure shown in the following formula I-11.
Formula I-11
In the formula I-11, n=5%, and m is p=0.8:1;
the weight average molecular weight of the binder L was 50 ten thousand.
Preparation example 12
The present preparation example provides a binder, specifically a binder Q, which is different from preparation example 1 in that the mass of acrylonitrile in the preparation method is adjusted to 1.448g, the mass of butadiene is adjusted to 10g, and the other is the same as preparation example 1.
The adhesive Q has a structure shown in the following formula I-12.
Formula I-12
In the formula I-12, n=5%, and m is p=0.15:1;
the weight average molecular weight of the binder Q was 50 ten thousand.
Preparation example 13
The present preparation example provides a binder, specifically a binder R, which is different from preparation example 1 in that the mass of acrylonitrile in the preparation method was adjusted to 8.678g, the mass of butadiene was adjusted to 10g, and the other is the same as preparation example 1.
The adhesive R has a structure shown in the following formula I-13.
Formula I-13
In the formula I-13, n=5%, and m is p=0.9:1;
the weight average molecular weight of the binder R is 50 ten thousand.
PREPARATION EXAMPLE 14
The present preparation example provides a binder, specifically a binder J, which is different from preparation example 1 in that the mass of vinylidene fluoride in the preparation method was adjusted to 2.765g, and the other is the same as in preparation example 1.
The adhesive J has a structure shown in the following formula I-14.
Formula I-14
In the formula I-14, n=25%, and m is p=0.6:1;
the weight average molecular weight of the binder J was 50 ten thousand.
Example 1
The embodiment provides positive electrode slurry, a preparation method and application, wherein the positive electrode slurry comprises the following components in parts by weight: sodium ion battery positive electrode material (layered transition metal oxide, sodium nickel iron manganate NaNi) 0.3 Fe 0.4 Mn 0.3 O 2 ) 73 parts of a binder (binder A provided in preparation example 1), 0.6 part of a conductive agent (conductive carbon black SP) 2 parts and 25 parts of a nonaqueous solvent (NMP).
The preparation method of the positive electrode slurry comprises the following steps:
(1) Mixing 0.6g of a binder A with 25g of a nonaqueous solvent, and sufficiently dissolving to obtain a binder solution;
(2) And (3) stirring 73g of the sodium ion battery positive electrode material, 2g of the conductive agent and the binder solution prepared in the step (1) fully to obtain the positive electrode slurry.
The embodiment provides a positive electrode plate, and the preparation method of the positive electrode plate is as follows: and coating the positive electrode slurry on the surface of an aluminum foil by using a doctor blade, and drying in a baking oven at 110 ℃ to prepare the positive electrode plate.
Example 2
The embodiment provides positive electrode slurry, a preparation method and application, wherein the positive electrode slurry comprises the following components in parts by weight: sodium ion battery anode material (Prussian blue type anode material, naFe (CN)) 6 ) 69 parts of a binder (binder B provided in preparation example 2), 2 parts of a conductive agent (carbon nanotubes), 1 part of a non-aqueous solvent (DMAC) and 28 parts of a non-aqueous solvent.
The preparation method of the positive electrode slurry comprises the following steps:
(1) Mixing 2g of a binder B and 28g of a nonaqueous solvent, and fully dissolving to obtain a binder solution;
(2) And (3) fully stirring 69 g sodium ion battery positive electrode material, 1g of conductive agent and the binder solution prepared in the step (1) to obtain the positive electrode slurry.
The embodiment provides a positive electrode plate, and the preparation method of the positive electrode plate is as follows: and coating the positive electrode slurry on the surface of an aluminum foil by using a doctor blade, and drying in a baking oven at 110 ℃ to prepare the positive electrode plate.
Example 3
The embodiment provides positive electrode slurry, a preparation method and application, wherein the positive electrode slurry comprises the following components in parts by weight: sodium ion battery positive electrode material (polyanion compound, na 4 Fe 2 (PO 4 ) 2 P 2 O 7 ) 75 parts of a binder (binder C provided in preparation example 3), 4 parts of a conductive agent (carbon black) and 20 parts of a nonaqueous solvent (DMSO).
The preparation method of the positive electrode slurry comprises the following steps:
(1) Mixing 4g of a binder C with 20g of a nonaqueous solvent, and fully dissolving to obtain a binder solution;
(2) And (3) fully stirring 75 g sodium ion battery positive electrode material, 4g of conductive agent and the binder solution prepared in the step (1) to obtain the positive electrode slurry.
The embodiment provides a positive electrode plate, and the preparation method of the positive electrode plate is as follows: and coating the positive electrode slurry on the surface of an aluminum foil by using a doctor blade, and drying in a baking oven at 110 ℃ to prepare the positive electrode plate.
Example 4
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder D provided in preparation example 4 of the same quality, and otherwise is the same as example 1.
Example 5
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder E provided in preparation example 5 of the same quality, and otherwise is the same as example 1.
Example 6
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder F provided in preparation example 6 of the same quality, and otherwise is the same as example 1.
Example 7
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder G provided in preparation example 7 of the same quality, and otherwise is the same as example 1.
Example 8
The present example provides a positive electrode slurry, a method of producing the same, and an application, which differ from example 1 only in that the weight part of the binder was adjusted to 0.3 part, and in the method of producing a positive electrode slurry, the mass of the binder a was adjusted to 0.3g, and the other steps were the same as in example 1.
Example 9
This example provides a positive electrode slurry, a method of producing the same, and an application thereof, which differ from example 1 only in that the weight part of the binder was adjusted to 4.5 parts, and in the method of producing a positive electrode slurry, the mass of the binder a was adjusted to 4.5g, and the other steps were the same as in example 1.
Example 10
This comparative example provides a positive electrode slurry and a production method and application, which differ from example 1 only in that the binder a is replaced with the binder H provided in production example 8 of the same quality, and otherwise is the same as example 1.
Example 11
This comparative example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder I provided in preparation example 9 of the same quality, and otherwise is the same as example 1.
Example 12
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder K provided in preparation example 10 of the same quality, and otherwise is the same as example 1.
Example 13
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder L provided in preparation example 11 of the same quality, and otherwise is the same as example 1.
Example 14
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder Q provided in preparation example 12 of the same quality, and otherwise is the same as example 1.
Example 15
This example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder R provided in preparation example 13 of the same quality, and otherwise is the same as example 1.
Comparative example 1
This comparative example provides a positive electrode slurry and a preparation method and application, which differ from example 1 only in that the binder a is replaced with the binder J provided in preparation example 14 of the same quality, and otherwise is the same as example 1.
Comparative example 2
This comparative example provides a positive electrode slurry and a preparation method and application, which are different from those of example 1 only in that the binder A is replaced with polyvinylidene fluoride (manufacturer: wu Yu, trade name: W1700) of the same quality, and the other is the same as that of example 1.
The following performance tests were performed on the positive electrode slurries and positive electrode sheets provided in examples and comparative examples.
(1) Viscosity of the positive electrode slurry: the viscosity of the positive electrode slurry was measured using a viscometer, the viscosity of the positive electrode slurry just prepared was measured and recorded as 0 hour slurry viscosity, the viscosity of the positive electrode slurry left at 25 ℃ for 4 hours was measured and recorded as 4 hours slurry viscosity, and the rate of change in viscosity was calculated.
(2) Gel properties of positive electrode slurry: placing the positive electrode slurry at 25 ℃ for 6 hours by adopting a visual method, taking 5mL of slurry by using an injection, injecting the slurry on the surface of an aluminum foil, and visually observing the slurry state, and if no flow occurs, regarding the slurry as gel; if it is flowable, it is considered not to be gelled.
(3) Flexibility of the positive pole piece: the cylindrical shaft bending experiment instrument is used, and the specific method is that the positive pole piece is cut into rectangular sample strips with the width of 5cm, then the rectangular sample strips are wound on a metal cylinder with the diameter of 4 mm, and the positive pole piece is pulled at a constant speed of 180 degrees, so that the state of the pole piece is observed. The good and bad of the flexibility of the pole piece are sequentially expressed as complete no crack, slight material drop, massive material drop and breaking from good to bad.
(4) Positive electrode sheet peel strength: reference is made to the national standard GB/T2790-1995.
(5) Thickness change rate: measuring the thickness d of the positive electrode plate prepared by coating the positive electrode slurry prepared on the surface of the aluminum foil by using a ten-thousandth ruler 1 Testing the thickness d of the positive electrode plate prepared by coating the positive electrode slurry on the surface of the aluminum foil after being placed for 4 hours at 25 DEG C 2 Thickness change rate= (d) 2 -d 1 )/d 1 ×100%。
The test results are shown in Table 1.
TABLE 1
According to the test results in Table 1, the positive electrode slurries provided in examples 1 to 15 are not gelled after being placed at 25 ℃ for 6 hours, and the viscosity change rate of the positive electrode slurry is 3.42% -26.99% after being placed at 25 ℃ for 4 hours, so that the slurry gelation phenomenon caused by long-term storage of the positive electrode slurry is effectively improved, the storage time of the positive electrode slurry is prolonged, and the viscosity stability of the positive electrode slurry is improved. The positive electrode slurries provided in examples 1 to 7 were not gelled when left at 25℃for 6 hours, and the viscosity change rate of the positive electrode slurries was 3.42% to 19.47% when left at 25℃for 4 hours, and were excellent in flexibility.
FIG. 1 is an infrared spectrum of the binder provided in preparation example 1, at 2235cm -1 There was a distinct-CN absorption peak at 1168cm -1 Has obvious C-F bond absorption peak at 2850 cm and 2916cm -1 With obvious-CH 2 Absorption peaks, it can thus be demonstrated that the prepared material is of the structure of formula I. FIG. 2 is a scanning electron microscope image of a coating layer formed by the positive electrode slurry on the positive electrode sheet according to example 1, from whichTherefore, the conductive agent and the positive electrode material of the sodium ion battery are better in dispersion condition, and no agglomeration condition exists.
In comparison with example 1, when the binder a was replaced with the binder D (example 4) provided in preparation example 4 of the same quality, the viscosity change rate was decreased, and it was confirmed that the binder having the structure shown in formula I, in which n=0, was the minimum viscosity change rate of the positive electrode slurry prepared.
As can be seen from a comparison of examples 1 and examples 4 to 7, the viscosity change rate of the positive electrode slurry obtained was increased as n was increased.
Compared with example 1, if the weight part of the binder is too small (example 8), the initial viscosity of the positive electrode slurry is increased and the viscosity change rate is large, because the binder cannot be completely covered on the surface of the positive electrode particles, the friction force received during shearing is large, the initial viscosity is large, the particles are settled with the increase of the standing time, the binder on the surface of the positive electrode particles is continuously reduced, the friction force received between the particles is further increased during shearing, the viscosity change rate is large, and the binder is small in adhesive force provided by the binder after the slurry is coated on the current collector, the peeling strength is low, and the problem of material dropping is easily caused because the amount of the binder is too small; if the weight fraction of the binder is too large (example 9), the prepared positive electrode slurry has a large initial viscosity, and the positive electrode sheet has poor flexibility although no gel, and it is proved that the positive electrode slurry prepared with the weight fraction of the binder in a specific range has better performance.
Compared with example 1, if the weight average molecular weight of the binder is too small (example 10), the initial viscosity of the positive electrode slurry is low, which is unfavorable for the stability of the slurry, and the coating and aluminum foil are easy to adhere and are not firm, and the pole piece is easy to drop; if the weight average molecular weight is too large (example 11), the initial viscosity of the positive electrode slurry is large, the flexibility of the pole piece after the pole piece is coated is poor, and the thickness stability of the coating is poor.
In comparison with example 1, when the adhesive a was replaced with the adhesive Q (example 14) provided in preparation example 12 of the same quality, the peel strength of the positive electrode sheet was lowered, and the adhesion of the coating layer formed of the positive electrode slurry to the foil was reduced; if the binder a is replaced with the binder R (example 15) provided in preparation example 13 of the same quality, the flexibility of the positive electrode sheet becomes poor, and it is proved that the compound having the structure shown in formula I, in which the ratio of m to p is 0.2 to 0.8, is used as the binder, and the prepared positive electrode slurry has better performance.
In comparison with example 1, if the binder a is replaced with the binder J (comparative example 1) provided in preparation example 14 of the same quality, the positive electrode slurry is liable to gel, resulting in poor coating thickness stability.
In comparison with example 1, if the binder a is replaced with polyvinylidene fluoride of the same mass (comparative example 2), the positive electrode slurry gel is the most serious and the coating thickness stability is the worst.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (9)
1. A positive electrode slurry, characterized in that the positive electrode slurry comprises a combination of a sodium ion battery positive electrode material, a binder, a conductive agent and a nonaqueous solvent;
the binder comprises a compound with a structure shown in a formula I;
i is a kind of
In the formula I, p is more than 0, m is more than 0, n is more than 0 and less than or equal to 20%, and p+m+n=100%;
the weight average molecular weight of the binder is 30 ten thousand to 100 ten thousand;
the preparation method of the adhesive comprises the following steps: under the condition of no water and no oxygen, adding a certain quantity of toluene, acrylonitrile and azodiisoheptonitrile into a reactor, slowly introducing butadiene and vinylidene fluoride under the stirring state, and making the reaction system react for a period of time at 70 DEG CQuenching and washing with methanol after the reaction is finished to prepare gel, dissolving the gel with butanone to prepare a primary product, preparing a glue solution, placing the glue solution into a high-pressure reaction kettle, and adding 0.002g of Rh (PPh) 3 ) 3 Cl is taken as a catalyst, hydrogen is replaced for 3 times, excessive hydrogen is slowly introduced, reaction is carried out under the pressure of 8 Mpa at 140 ℃, 4 h is carried out, cooling is carried out, ethanol gel is used, condensate is obtained, and the condensate is dried under the condition of 50 ℃ for 10 h, thus obtaining the binder;
the ratio of m to p is 0.2-0.6:1.
2. The positive electrode slurry according to claim 1, wherein the sodium ion battery positive electrode material comprises any one or a combination of at least two of layered transition metal oxide, prussian blue-based positive electrode material, or polyanion-based compound;
the chemical formula of the layered transition metal oxide is NaM x O y Wherein M is selected from one or a combination of at least two of iron, copper, nickel, cobalt or manganese, x is more than or equal to 0.8 and less than or equal to 1.5, y is more than or equal to 1.5 and less than or equal to 2.5, and the values of x and y meet the chemical formula charge balance;
the structural general formula of the polyanion compound is Na a M' b (XO 4 ) c Y d Wherein M' is any one or a combination of at least two of Fe, mn, V, cr, ti, ni or Co, X is Si and/or P, Y is F and/or P 2 O 7 ，0<a<5.0，0<b<4.0，0<c<4.0，0<d<4.0。
3. The positive electrode slurry according to claim 1, wherein the conductive agent comprises carbon nanotubes and/or carbon black;
the carbon black is conductive carbon black SP.
4. The positive electrode slurry according to claim 1, wherein the nonaqueous solvent comprises any one or a combination of at least two of N-methylpyrrolidone, dimethylacetamide, and dimethylsulfoxide.
5. The positive electrode slurry according to claim 1, wherein the positive electrode slurry comprises the following components in parts by weight: 69-75 parts of sodium ion battery anode material, 0.5-4 parts of binder, 0.1-4 parts of conductive agent and 20-28 parts of nonaqueous solvent.
6. The positive electrode slurry according to claim 1, wherein the positive electrode slurry has a viscosity change rate of not more than 20% when left at 25 ℃ of 4 h.
7. A method for producing the positive electrode slurry according to any one of claims 1 to 6, comprising the steps of: and mixing the sodium ion battery anode material, the binder, the conductive agent and the nonaqueous solvent to obtain the anode slurry.
8. The positive electrode plate is characterized by comprising a current collector and a coating covered on the current collector, wherein the coating is prepared from the positive electrode slurry according to any one of claims 1-6.
9. A sodium ion battery comprising the positive electrode sheet of claim 8.
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