CN117133921A - Sodium ion battery negative electrode slurry, pole piece and pole piece preparation method - Google Patents
Sodium ion battery negative electrode slurry, pole piece and pole piece preparation method Download PDFInfo
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- CN117133921A CN117133921A CN202311397015.1A CN202311397015A CN117133921A CN 117133921 A CN117133921 A CN 117133921A CN 202311397015 A CN202311397015 A CN 202311397015A CN 117133921 A CN117133921 A CN 117133921A
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- negative electrode
- ion battery
- sodium ion
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- sodium
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 90
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 40
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011888 foil Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021385 hard carbon Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 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 claims description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000007581 slurry coating method Methods 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 238000009835 boiling Methods 0.000 abstract description 7
- 238000009957 hemming Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 239000002305 electric material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000006257 cathode slurry Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000000306 component Substances 0.000 description 9
- 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 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000000693 micelle Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a sodium ion battery negative electrode slurry, a pole piece and a pole piece preparation method, which belong to the technical field of electric material chemistry, wherein the sodium ion battery negative electrode slurry comprises the following components in percentage by mass: 90% -99% of negative electrode active material; 2% -5% of a conductive agent; 1% -3% of dispersing agent; 2% -5% of binder; and 0.1% -5% of an additive; wherein the additive is sodium stearate powder. The sodium ion battery negative electrode plate is prepared from the sodium ion battery negative electrode slurry. The preparation method of the sodium ion battery negative electrode plate is used for preparing the electrode plate. The application is based on adding sodium stearate, and can further prevent edge shrinkage phenomenon when the slurry is coated on the surface of a current collector by adjusting the surface tension of the slurry, and can increase the boiling point of the slurry, thereby improving the phenomena of reduced coating adhesion, pole piece material falling and hemming after baking caused by binder migration during drying.
Description
Technical Field
The application relates to the technical field of electric material chemistry, in particular to a sodium ion battery negative electrode slurry, a pole piece and a pole piece preparation method.
Background
The Sodium-ion battery (rechargeable battery) is a secondary battery (rechargeable battery), has the advantages of low price and rich reserve, and can be used in the fields of energy storage systems, low-speed electric vehicles and the like. The negative electrode is one of the core components of the battery core of the sodium battery, and is different from a lithium battery, sodium ions do not form alloy with aluminum, so that the negative electrode of the sodium battery can use aluminum foil as a current collector, and both the positive electrode and the negative electrode use the aluminum foil as the current collector, so that the sodium battery has no overdischarge characteristic, can discharge to 0V, and the cost is reduced.
However, deionized water is generally adopted as a solvent for the negative electrode of the sodium ion battery, and the surface wetting tension of the aluminum foil is small, so that the slurry of the pole piece is easy to shrink and curl in the coating process, the coated pole piece is brittle, is easy to crack and drop, and is easy to cause the performance reduction and the potential safety hazard of the sodium ion battery.
In order to overcome the defects of easy hemming and cracking of the negative electrode sheet, a lithium battery is usually added with a small amount of high-boiling-point and difficult-to-volatilize N-methylpyrrolidone when preparing negative electrode slurry, however, the N-methylpyrrolidone is difficult to completely remove when the negative electrode sheet is heated and dried, and residual N-methylpyrrolidone is adsorbed on the surface of graphite, so that SEI film and graphite are combined insecurely, and the cycle performance of the battery is adversely affected; and the recovery difficulty of N-methyl pyrrolidone is high, and the N-methyl pyrrolidone is easy to cause environmental pollution after being discharged and is harmful to human bodies.
In the prior art, the patent CN114335542A remarkably improves the cracking phenomenon of the lithium battery negative electrode sheet by preparing a mixture of a water-soluble (methyl) acrylate monomer, a water-soluble vinyl monomer and a water-soluble linear oligomer as an additive, but in the patent, the additive is complex to prepare, has great difficulty and has higher cost; the patent CN114335491A is characterized in that silicon carbon is added as a second main material, the two main materials are mixed step by step, then the two slurries are mixed, the stability of the lithium battery cathode slurry is improved, the edge curling cracking of a coating edge, the cracking and decarburization phenomena of a coating area are improved, but the first slurry and the second slurry are required to be respectively obtained by mixing, the mixing is carried out, the process is complex and time-consuming, and the final practical effect is not ideal; the patent CN115986115A effectively improves the cracking and curling phenomena of the coated pole piece of the lithium battery negative electrode by adding the modified silicone oil composition aqueous solution as an additive, but the technology is characterized in that the modified silicone oil composition aqueous solution is required to be mixed separately and then added, thereby being not beneficial to the mass production operation of the negative electrode piece and being difficult to be applied industrially.
In addition, patent CN114335542a, patent CN114335491a and patent CN115986115A all relate to the field of lithium electronics, and the scheme is applied to the lithium battery negative electrode sheet, and the lithium battery negative electrode adopts copper foil as current collector, and because copper foil surface wetting tension is far greater than the aluminium foil, the cracking and curling phenomenon of the lithium battery negative electrode sheet are lighter, and the improvement scheme applicable to the lithium battery negative electrode can not be fully effective on sodium battery, so that the scheme can not be applied to the technical field of sodium ion battery.
In view of this, it is necessary to design a corresponding negative electrode material for the structural characteristics of the sodium ion battery to ensure the performance and stability of the sodium ion negative electrode sheet.
Disclosure of Invention
The application aims to provide sodium ion battery negative electrode slurry, which is based on the addition of sodium stearate, so that edge shrinkage phenomenon does not occur after slurry coating by adjusting the surface tension of the slurry, and on the other hand, the phenomena of coating adhesion reduction, pole piece material falling and curling after baking caused by binder migration during drying are improved by increasing the boiling point of the slurry. Meanwhile, the application also provides a sodium ion negative electrode plate and a preparation method thereof based on the sodium ion battery negative electrode slurry.
One of the purposes of the application is mainly achieved by the following technical scheme: the sodium ion battery cathode slurry consists of the following components in percentage by mass:
90% -99% of negative electrode active material;
2% -5% of a conductive agent;
1% -3% of dispersing agent;
2% -5% of binder; the method comprises the steps of,
0.1% -5% of additive;
wherein the additive is sodium stearate powder.
Based on the technical scheme, the sodium ion battery anode slurry consists of the following components in percentage by mass:
93% of a negative electrode active material;
2% of a conductive agent;
1.5% dispersant;
2.5% binder; the method comprises the steps of,
1% of additive.
Based on the technical scheme, the anode active material is hard carbon, soft carbon or soft and hard carbon composite material.
Based on the technical scheme, the conductive agent is any one or a mixture of more than two of conductive carbon black, acetylene black and carbon nano tubes.
Based on the technical scheme, the dispersing agent is sodium carboxymethyl cellulose powder or polyacrylic acid.
Based on the technical scheme, the binder is styrene-butadiene rubber emulsion.
Compared with the prior art, the application has the following beneficial effects: according to the sodium ion battery negative electrode slurry, sodium stearate is introduced into the slurry as an additive, so that edge shrinkage phenomenon does not occur after the slurry is coated by adjusting the surface tension of the slurry, and the phenomena of coating adhesion force reduction, pole piece material dropping and hemming after baking, which are caused by binder migration during drying, are improved by increasing the boiling point of the slurry.
The second purpose of the application is mainly realized by the following technical scheme: the negative electrode plate of the sodium ion battery comprises a current collector and a negative electrode active material layer coated on at least one side of the current collector, wherein the negative electrode active material layer is prepared from the negative electrode slurry of the sodium ion battery.
Based on the technical scheme, the current collector is carbon-coated aluminum foil, double-light aluminum foil or corrosion aluminum foil.
According to the sodium ion battery negative electrode plate, the sodium stearate is added, so that the matching performance of the slurry and the surface wetting tension of the current collector is effectively improved, the phenomena of material falling and curling of the baked electrode plate are improved, and the sodium ion battery negative electrode plate has the characteristics of uniform coating thickness and strong adhesion.
The third object of the application is mainly achieved by the following technical scheme: the preparation method of the sodium ion battery negative electrode plate comprises the following steps:
the method comprises the steps of (1) putting a negative electrode active material, a conductive agent, a dispersing agent, a binder, an additive and a solvent into an electrode slurry stirring tank according to a certain proportion, stirring uniformly, vacuumizing, defoaming and filtering to obtain sodium ion battery negative electrode slurry;
coating the prepared sodium ion battery negative electrode slurry on a current collector with the slurry;
and (5) drying the current collector after the slurry coating is finished, and thus obtaining the composite material.
Based on the preparation method, the solvent is deionized water.
Based on the preparation methodThe viscosity of the sodium ion battery cathode slurry is 2000-5000 mPa.s, the thickness of the coating on the current collector is 50-200 mu m, and the surface density of the coating on one side of the current collector is 4-23mg/cm 2 。
According to the preparation method, sodium stearate is added in the slurry preparation process, no extra step is introduced, the preparation method is easy to realize, the preparation method has the advantages of simplicity in operation and low cost, no other harmful substances are generated in the whole preparation process, the preparation method is environment-friendly and safe, the defects that the adhesive force is poor, the pole piece is easy to drop and turn-up can be overcome, as sodium stearate simultaneously has nonpolar groups and polar groups, the sodium stearate can be dissolved in the slurry to play a role of a surfactant, the polar groups of the sodium stearate have hydrophilicity, the nonpolar groups are mutually close to form micelle groups with nonpolar groups outwards and polar ends inwards, the micelle groups are uniformly distributed on the surface of the slurry to form a molecular film with nonpolar groups outwards when the concentration of the micelle groups reaches a critical concentration, the surface tension of the slurry is reduced, the edge shrinkage phenomenon does not occur when the slurry is coated on the surface of a current collector, in addition, the sodium stearate can improve the boiling point of water, the evaporation rate of the aqueous slurry during the coating heating and drying process is reduced, the phenomena of coating adhesive force reduction, the pole piece dropping and turn-up are reduced, the preparation efficiency and the industrial application range of the pole piece are improved, and the preparation method is convenient to popularize in a large scale.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a flow chart of a method of preparing a sodium ion battery negative electrode slurry;
fig. 2 is a graph showing the cycle performance of the sodium ion batteries prepared in comparative example 1, comparative example 2 and example 2, respectively;
FIG. 3 is an effect diagram of the negative electrode tab of the sodium ion battery prepared in example 2;
FIG. 4 is an effect diagram of the negative electrode tab of the sodium ion battery prepared in comparative example 1;
Detailed Description
The present application will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present application more apparent, and the description thereof is merely illustrative of the present application and not intended to be limiting.
The embodiment of the application provides a sodium ion battery negative electrode slurry, which comprises the following components in percentage by mass:
90% -99% of negative electrode active material;
2% -5% of a conductive agent;
1% -3% of dispersing agent;
2% -5% of binder; the method comprises the steps of,
0.1% -5% of additive;
wherein the additive is sodium stearate powder.
In the prior art, deionized water is generally adopted as a solvent for a negative electrode of a sodium ion battery, and the surface wetting tension of an aluminum foil is small, so that slurry of a pole piece is easy to shrink and turn up in the coating process, the coated pole piece is brittle, is easy to crack and drop, and is easy to cause performance degradation of the sodium ion battery and potential safety hazard. Based on the above, sodium stearate is introduced into the slurry as an additive in the sodium ion battery cathode slurry in the embodiment, so that on one hand, edge shrinkage phenomenon does not occur after the slurry is coated by adjusting the surface tension of the slurry, and on the other hand, the phenomena of coating adhesion reduction, pole piece material falling and curling after baking caused by binder migration during drying are improved by increasing the boiling point of the slurry.
And by adding sodium stearate, the matching of the surface wetting tension of the slurry and the foil can be effectively improved in the subsequent pole piece preparation process, the phenomena of pole piece material dropping and hemming after baking are improved, and the preparation of the sodium ion battery negative pole piece with uniform coating thickness and strong adhesion is facilitated.
The sodium stearate is white solid powder, is widely applied to metal heat treatment and plastic stabilizer, is also used for manufacturing soap detergents, and is used as an emulsifier in cosmetics, as the sodium stearate simultaneously has nonpolar groups and polar groups, the sodium stearate can be dissolved in slurry to play a role of a surfactant, when the sodium stearate is applied, the polar groups have hydrophilicity, the nonpolar groups are mutually close to form micelle groups with nonpolar groups outwards and polar ends inwards, when the concentration of the micelle groups reaches a critical concentration, molecular films with the nonpolar groups outwards are uniformly distributed on the surface of the slurry, so that the surface tension of the slurry can be reduced, the edge shrinkage phenomenon does not occur when the slurry is coated on the surface of a current collector, in addition, the sodium stearate is added, the boiling point of water can be increased, the evaporation rate of the aqueous slurry during the heating and drying of the coating can be reduced, the coating adhesion force reduction, the pole piece material dropping and the curling phenomenon caused by the migration of a binder can be further ensured, finally, the sodium stearate is solid insoluble after the drying, and the negative electrode piece of a sodium stearate is not influenced by the negative electrode piece of an electrolyte.
In specific implementation, the sodium ion battery anode slurry consists of the following components in percentage by mass:
93% of a negative electrode active material;
2% of a conductive agent;
1.5% dispersant;
2.5% binder; the method comprises the steps of,
1% of additive.
In a specific implementation, the negative electrode active material is hard carbon, soft carbon or a soft and hard carbon composite material.
In specific implementation, the conductive agent is any one or a mixture of more than two of conductive carbon black (Super P), acetylene black and Carbon Nanotubes (CNTs).
In a specific implementation, the dispersant is sodium carboxymethyl cellulose (CMC) powder or polyacrylic acid (PAA).
In a specific implementation, the binder is a Styrene Butadiene Rubber (SBR) emulsion.
The embodiment of the application also provides a negative electrode plate of the sodium ion battery, which comprises a current collector and a negative electrode active material layer coated on at least one side of the current collector, wherein the negative electrode active material layer is prepared from the negative electrode slurry of the sodium ion battery. According to the sodium ion battery negative electrode plate, the sodium stearate is added, so that the matching property of the slurry and the surface wetting tension of the current collector is effectively improved, the phenomena of material falling and curling of the baked electrode plate are improved, and the sodium ion battery negative electrode plate has the characteristics of uniform coating thickness and strong adhesion
In specific implementation, the current collector is carbon-coated aluminum foil, double-light aluminum foil or corrosion aluminum foil.
As shown in fig. 1, the embodiment of the application also provides a preparation method of the sodium ion battery negative electrode plate, which comprises the following steps:
s1, putting a negative electrode active material, a conductive agent, a dispersing agent, a binder, an additive and a solvent into an electrode slurry stirring tank according to a proportion, stirring uniformly, vacuumizing, defoaming and filtering to obtain a sodium ion battery negative electrode slurry;
s2, coating the prepared sodium ion battery negative electrode slurry on a current collector;
and S3, drying the current collector after the slurry coating is completed, and obtaining the composite material.
According to the preparation method disclosed by the application, sodium stearate is added in the slurry preparation process, no extra step is introduced, the preparation method is easy to realize, the preparation method has the advantages of simplicity in operation and low cost, no other harmful substances are generated in the whole preparation process, the preparation method is environment-friendly and safe, the defects of poor adhesion, easiness in material dropping and hemming of a pole piece can be overcome, and as sodium stearate simultaneously has nonpolar groups and polar groups, sodium stearate can be dissolved in the slurry to play a role of a surfactant, the polar groups of the sodium stearate have hydrophilicity, the nonpolar groups are mutually close to form micelle groups with nonpolar groups outwards and polar ends inwards, the micelle groups are uniformly distributed on the surface of the slurry to form a molecular film with nonpolar groups outwards when the concentration of the micelle groups reaches a critical concentration, the surface tension of the slurry is reduced, the edge shrinkage phenomenon does not occur when the slurry is coated on the surface of a current collector, in addition, the boiling point of water can be increased, the evaporation rate of the aqueous slurry is reduced, the phenomena of coating adhesion, material dropping and hemming caused by the adhesive are reduced, the polar pieces are facilitated to be reduced, the preparation efficiency and the preparation method is convenient to popularize in industrial application range, and the preparation efficiency of the pole piece is improved.
In a specific implementation, in the step S1, the solvent is deionized water.
In the specific implementation, in the step S2, the viscosity of the sodium ion battery anode slurry is 2000-5000 mPa.s, the thickness of the coating on the current collector is 50-200 mu m, and the surface density of the single-sided coating on the current collector is 4-23mg/cm 2 。
For a further understanding and appreciation of the application, the application will be further explained and illustrated below in connection with specific examples.
Example 1:
the sodium ion battery cathode slurry A consists of the following components in percentage by mass:
93.2% hard carbon;
2% conductive carbon black;
1.5% sodium carboxymethyl cellulose powder;
2.5% styrene-butadiene rubber emulsion; the method comprises the steps of,
0.8% sodium stearate powder.
Preparation of sodium ion battery negative electrode slurry A:
adding hard carbon, conductive carbon black and sodium carboxymethyl cellulose powder into a stirring tank according to mass proportion, adding sodium stearate powder according to corresponding proportion, and stirring uniformly to obtain negative electrode mixed material powder;
adding deionized water serving as a solvent into the powder of the anode mixed material, stirring and kneading, adding a proper amount of deionized water after kneading is finished, and continuously stirring until the viscosity of the mixture reaches 2000-5000 mPa.s;
and (3) pouring the styrene-butadiene rubber emulsion into a stirring tank according to the mass ratio, continuously stirring at a low speed until the emulsion is uniform, and filtering the emulsion by adopting a 100-mesh screen after vacuum defoaming.
Preparing a sodium ion battery negative electrode plate based on the sodium ion battery negative electrode slurry A:
the obtained sodium ion battery cathode slurry A is coated on a carbon-coated aluminum foil with the thickness of 12 mu m by an extrusion coater, and the single-sided density is 6mg/cm 2 Drying at 90deg.C.
Example 2:
the sodium ion battery cathode slurry B consists of the following components in percentage by mass:
93% hard carbon;
2% conductive carbon black;
1.5% sodium carboxymethyl cellulose powder;
2.5% styrene-butadiene rubber emulsion; the method comprises the steps of,
1% sodium stearate powder.
Preparation of sodium ion battery negative electrode slurry B:
adding hard carbon, conductive carbon black and sodium carboxymethyl cellulose powder into a stirring tank according to mass proportion, adding sodium stearate powder according to corresponding proportion, and stirring uniformly to obtain negative electrode mixed material powder;
adding deionized water serving as a solvent into the powder of the anode mixed material, stirring and kneading, adding a proper amount of deionized water after kneading is finished, and continuously stirring until the viscosity of the mixture reaches 2000-5000 mPa.s;
and (3) pouring the styrene-butadiene rubber emulsion into a stirring tank according to the mass ratio, continuously stirring at a low speed until the emulsion is uniform, and filtering the emulsion by adopting a 100-mesh screen after vacuum defoaming.
Preparing a sodium ion battery negative electrode plate based on the sodium ion battery negative electrode slurry B:
the obtained sodium ion battery cathode slurry B is coated on a carbon-coated aluminum foil with the thickness of 12 mu m by an extrusion coater, and the single-sided density is 6mg/cm 2 Drying at 90deg.C.
Example 3:
the sodium ion battery cathode slurry C consists of the following components in percentage by mass:
92.8% hard carbon;
2% conductive carbon black;
1.5% polyacrylic acid;
2.7% styrene-butadiene rubber emulsion; the method comprises the steps of,
1% sodium stearate powder.
Preparation of sodium ion battery negative electrode slurry C:
adding polyacrylic acid glue solution and part of deionized water into a stirring tank according to mass proportion, and stirring to obtain glue solution;
putting conductive carbon black powder into a stirring tank according to mass proportion, and stirring to obtain conductive glue solution;
putting hard carbon powder into a stirring tank according to mass proportion, and stirring to obtain a negative electrode mixture;
adding sodium stearate powder in a corresponding proportion into a stirring tank, and stirring uniformly;
adding proper amount of deionized water according to the proportion, and continuously stirring until the viscosity of the mixture reaches 2000-5000 mPa.s;
and (3) pouring the styrene-butadiene rubber emulsion into a stirring tank according to the mass ratio, continuously stirring at a low speed until the emulsion is uniform, and filtering the emulsion by adopting a 100-mesh screen after vacuum defoaming.
Preparing a sodium ion battery negative electrode plate based on the sodium ion battery negative electrode slurry C:
the obtained sodium ion battery cathode slurry C is coated on a carbon-coated aluminum foil with the thickness of 12 mu m by an extrusion coater, and the single-sided density is 6mg/cm 2 Drying at 90deg.C.
Comparative example 1:
the sodium ion battery cathode slurry D consists of the following components in percentage by mass:
94% hard carbon;
2% conductive carbon black;
1.5% sodium carboxymethyl cellulose;
2.5% styrene-butadiene rubber emulsion;
preparation of sodium ion battery negative electrode slurry D:
adding hard carbon, conductive carbon black and sodium carboxymethyl cellulose powder into a stirring tank according to mass proportion, and stirring to obtain negative electrode mixed material powder;
adding deionized water into the negative electrode mixed material powder, stirring and kneading, adding a proper amount of deionized water after kneading is finished, and continuously stirring until the viscosity of the mixture reaches 2000-5000 mPa.s;
and (3) pouring the styrene-butadiene rubber emulsion into a stirring tank according to the mass ratio, continuously stirring at a low speed until the emulsion is uniform, and filtering the emulsion by adopting a 100-mesh screen after vacuum defoaming.
Preparing a sodium ion battery negative electrode plate based on the sodium ion battery negative electrode slurry D:
the obtained sodium ion battery negative electrode slurry D is coated on a carbon-coated aluminum foil with the thickness of 12 mu m by an extrusion coater, and the single-sided density is 6mg/cm 2 Oven drying at 80deg.C.
Comparative example 2:
the sodium ion battery cathode slurry E consists of the following components in percentage by mass:
93% hard carbon;
2% conductive carbon black;
1.5% sodium carboxymethyl cellulose;
2.5% styrene-butadiene rubber emulsion; the method comprises the steps of,
1% N-methylpyrrolidone
Preparation of sodium ion battery negative electrode slurry E:
adding hard carbon, conductive carbon black and sodium carboxymethyl cellulose powder into a stirring tank according to mass proportion, and stirring to obtain negative electrode mixed material powder;
adding deionized water into the negative electrode mixed material powder, stirring and kneading, adding a proper amount of deionized water after kneading is finished, and continuously stirring until the viscosity of the mixture reaches 2000-5000 mPa.s;
and (3) pouring the styrene-butadiene rubber emulsion into a stirring tank according to the mass ratio, continuously stirring at a low speed until the emulsion is uniform, and filtering the emulsion by adopting a 100-mesh screen after vacuum defoaming.
Preparing a sodium ion battery negative electrode plate based on the sodium ion battery negative electrode slurry E:
the obtained sodium ion battery negative electrode slurry E is coated on a carbon-coated aluminum foil with the thickness of 12 mu m by an extrusion coater, and the single-sided density is 6mg/cm 2 Drying at 90deg.C.
By performing the corresponding pole piece detection after coating for the above examples 1-3, comparative examples 1-2, the following table one data was obtained:
table one: examples 1-3, comparative examples 1-2 data sheet after coating
From Table one can see:
in examples 1-3, sodium stearate was added, the peel strength of the pole pieces prepared from the three was significantly improved, and the edge-bulging and material-dropping phenomena were also significantly improved, whereas in comparative examples 1-2, sodium stearate was not added, and it can be seen that the sodium battery negative electrode slurry without sodium stearate was poor in coating state, and the prepared negative electrode pieces all had thick edges and material-dropping phenomena.
Comparative example 1 and comparative example 2 are identical in composition and preparation to example 2 except that sodium stearate is not added to comparative example 1 and that the additive of comparative example 2 is 1% N-methylpyrrolidone.
Fig. 2 is a graph showing the cycle performance of the sodium ion batteries prepared in comparative example 1, comparative example 2 and example 2, respectively, in which the capacity retention rate of the sodium ion battery of comparative example 1 after 50 cycles at 0.5C was 89.11%, the capacity retention rate of the sodium ion battery of comparative example 2 after 50 cycles at 0.2C was 85.67%, and the capacity retention rate of the sodium ion battery of example 2 prepared after adding 1% sodium stearate after 50 cycles at 0.2C was 91.41%.
Further, with reference to fig. 3 and 4, it can be obtained that: the problem that the coating of the negative plate of the sodium battery is easy to bulge and drop can be solved by adding a proper amount of sodium stearate, the problem of the reduction of the circulation capacity retention rate caused by adding N-methyl pyrrolidone is solved, meanwhile, the polarization phenomenon in the charge and discharge of the sodium battery is improved due to the improvement of the stripping strength of the negative plate, the stability of the circulation capacity of the sodium battery is improved, and the sodium ion battery prepared by the method has better circulation performance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. The sodium ion battery negative electrode slurry is characterized by comprising the following components in percentage by mass:
90% -99% of negative electrode active material;
2% -5% of a conductive agent;
1% -3% of dispersing agent;
2% -5% of binder; the method comprises the steps of,
0.1% -5% of additive;
wherein,
the additive is sodium stearate powder.
2. The sodium ion battery anode slurry according to claim 1, which is characterized by comprising the following components in percentage by mass:
93% of a negative electrode active material;
2% of a conductive agent;
1.5% dispersant;
2.5% binder; the method comprises the steps of,
1% of additive.
3. The negative electrode slurry for sodium ion battery according to claim 1, wherein the negative electrode active material is hard carbon, soft carbon or soft and hard carbon composite material.
4. The negative electrode slurry for sodium ion battery according to claim 1, wherein the conductive agent is any one or a mixture of two or more of conductive carbon black, acetylene black and carbon nanotubes.
5. The negative electrode slurry for sodium ion battery according to claim 1, wherein the dispersant is sodium carboxymethyl cellulose powder or polyacrylic acid.
6. The sodium ion battery negative electrode slurry of claim 1, wherein the binder is a styrene-butadiene rubber emulsion.
7. A negative electrode plate of a sodium ion battery, comprising a current collector and a negative electrode active material layer coated on at least one side of the current collector, wherein the negative electrode active material layer is made of the negative electrode slurry of the sodium ion battery according to any one of claims 1 to 6.
8. The negative electrode tab of sodium ion battery of claim 7, wherein the current collector is carbon coated aluminum foil, double light aluminum foil or etched aluminum foil.
9. A method for preparing the negative electrode plate of the sodium ion battery as claimed in claim 7, comprising the following steps:
the method comprises the steps of (1) putting a negative electrode active material, a conductive agent, a dispersing agent, a binder, an additive and a solvent into an electrode slurry stirring tank according to a certain proportion, stirring uniformly, vacuumizing, defoaming and filtering to obtain sodium ion battery negative electrode slurry;
coating the prepared sodium ion battery negative electrode slurry on a current collector with the slurry;
and (5) drying the current collector after the slurry coating is finished, and thus obtaining the composite material.
10. The preparation method according to claim 9, wherein the sodium ion battery negative electrode slurry has a viscosity of 2000-5000 mpa.s, a thickness of 50-200 μm coated on the current collector, and a surface density of 4-23mg/cm coated on one side of the current collector 2 。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010025979A (en) * | 1999-09-02 | 2001-04-06 | 김순택 | Composition of active material for lithium secondary batteries |
| CN110591613A (en) * | 2019-09-07 | 2019-12-20 | 河南平煤国能锂电有限公司 | Binder for lithium ion battery cathode and preparation method thereof |
| WO2020145295A1 (en) * | 2019-01-11 | 2020-07-16 | 株式会社クラレ | Non-aqueous electrolyte cell electrode binder, non-aqueous electrolyte cell electrode binder solution, non-aqueous electrolyte cell electrode slurry, non-aqueous electrolyte cell electrode, and non-aqueous electrolyte cell |
| CN112786843A (en) * | 2021-02-02 | 2021-05-11 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
| CN115799443A (en) * | 2023-02-06 | 2023-03-14 | 中自环保科技股份有限公司 | Sodium ion battery microporous aluminum foil electrode and preparation method thereof |
| CN116454233A (en) * | 2023-04-18 | 2023-07-18 | 湖南领湃新能源科技有限公司 | Preparation method of sodium ion battery negative electrode slurry and sodium ion battery |
| WO2023174335A1 (en) * | 2022-03-15 | 2023-09-21 | 湖北亿纬动力有限公司 | Negative electrode slurry composition and use thereof |
| CN116799206A (en) * | 2023-05-06 | 2023-09-22 | 维科技术股份有限公司 | Sodium ion battery negative electrode slurry and sodium ion battery negative electrode plate |
-
2023
- 2023-10-26 CN CN202311397015.1A patent/CN117133921A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010025979A (en) * | 1999-09-02 | 2001-04-06 | 김순택 | Composition of active material for lithium secondary batteries |
| WO2020145295A1 (en) * | 2019-01-11 | 2020-07-16 | 株式会社クラレ | Non-aqueous electrolyte cell electrode binder, non-aqueous electrolyte cell electrode binder solution, non-aqueous electrolyte cell electrode slurry, non-aqueous electrolyte cell electrode, and non-aqueous electrolyte cell |
| CN110591613A (en) * | 2019-09-07 | 2019-12-20 | 河南平煤国能锂电有限公司 | Binder for lithium ion battery cathode and preparation method thereof |
| CN112786843A (en) * | 2021-02-02 | 2021-05-11 | 天能电池集团股份有限公司 | Low-temperature lead storage battery negative electrode lead paste and negative plate |
| WO2023174335A1 (en) * | 2022-03-15 | 2023-09-21 | 湖北亿纬动力有限公司 | Negative electrode slurry composition and use thereof |
| CN115799443A (en) * | 2023-02-06 | 2023-03-14 | 中自环保科技股份有限公司 | Sodium ion battery microporous aluminum foil electrode and preparation method thereof |
| CN116454233A (en) * | 2023-04-18 | 2023-07-18 | 湖南领湃新能源科技有限公司 | Preparation method of sodium ion battery negative electrode slurry and sodium ion battery |
| CN116799206A (en) * | 2023-05-06 | 2023-09-22 | 维科技术股份有限公司 | Sodium ion battery negative electrode slurry and sodium ion battery negative electrode plate |
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