CN117374406A - Method for preparing sodium battery - Google Patents
Method for preparing sodium battery Download PDFInfo
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- CN117374406A CN117374406A CN202311190000.8A CN202311190000A CN117374406A CN 117374406 A CN117374406 A CN 117374406A CN 202311190000 A CN202311190000 A CN 202311190000A CN 117374406 A CN117374406 A CN 117374406A
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- 239000011734 sodium Substances 0.000 title claims abstract description 38
- 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 title claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 19
- 239000006258 conductive agent Substances 0.000 claims abstract description 62
- 239000011267 electrode slurry Substances 0.000 claims abstract description 62
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000010959 steel Substances 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 238000004804 winding Methods 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 130
- 239000000843 powder Substances 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 238000009775 high-speed stirring Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000006183 anode active material Substances 0.000 claims description 3
- 239000011884 anode binding agent Substances 0.000 claims description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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
- 229920000447 polyanionic polymer Polymers 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- 239000011888 foil Substances 0.000 description 20
- 238000005096 rolling process Methods 0.000 description 20
- 230000001105 regulatory effect Effects 0.000 description 17
- 229910001415 sodium ion Inorganic materials 0.000 description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 13
- 229910021385 hard carbon Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000003292 glue Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 238000009736 wetting Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000013543 active substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002706 dry binder Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of a sodium battery, which comprises the following steps: step S10: preparing positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate; the positive electrode slurry comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder, wherein the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (70-90): 2-5; step S20: preparing negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to form a negative electrode plate; the negative electrode slurry comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, wherein the mass ratio of the negative electrode active material to the negative electrode conductive agent to the negative electrode binder is (70-90): 2-5; step S30: and adding a diaphragm between the positive plate and the negative plate for winding, filling the positive plate and the negative plate into a steel shell, and sealing the steel shell after electrolyte is injected to form the sodium battery. The sodium battery prepared by the invention has excellent energy density, cycle stability and safety.
Description
[ field of technology ]
The invention relates to the technical field of batteries, in particular to a preparation method of a sodium battery.
[ background Art ]
In recent years, global new energy automobiles develop rapidly, and the high-speed increase of the demand of lithium ion batteries is driven. However, due to the shortage of lithium resources, the recent market for lithium ion batteries is also affected by the rising price of raw materials and the shortage of supply, and thus, there is an urgent need for new battery schemes to replace lithium batteries.
In recent two years, the industrialization process of sodium ion batteries has been rapidly developed, and the sodium ion batteries are widely used as ideal batteries for low-speed electric vehicles and large-scale energy storage systems in the future due to the remarkable advantages of abundant sodium salt reserves, low raw material cost, high quick charge rate, excellent high-low temperature performance and the like, and the working principle and the manufacturing process flow of the sodium batteries are very similar to those of the lithium ion batteries.
The existing sodium ion battery is inferior to a lithium ion battery in mass energy density and volume energy density, and the sodium ion battery is poor in circulation stability. Sodium ion batteries have a slow rate of application in large-scale commercial applications due to their low energy density and poor cycling stability. How to increase the energy density of sodium ion batteries is becoming a great concern for researchers, so it is necessary to develop a sodium battery with high battery capacity, good cycling stability and good safety.
[ invention ]
The invention aims to provide a preparation method of a sodium battery, and the prepared sodium battery has excellent energy density, cycle stability and safety.
In order to achieve the above object, the present invention provides a method for preparing a sodium battery, comprising the steps of: step S10: preparing positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate; the positive electrode slurry comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder, wherein the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (70-90): 2-5; step S20: preparing negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to form a negative electrode plate; the negative electrode slurry comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, wherein the mass ratio of the negative electrode active material to the negative electrode conductive agent to the negative electrode binder is (70-90): 2-5; step S30: and adding a diaphragm between the positive plate and the negative plate for winding, filling the positive plate and the negative plate into a steel shell, and sealing the steel shell after electrolyte is injected to form the sodium battery.
In a preferred embodiment, the positive electrode active material includes any one or more of layered transition metal oxides, prussian blue/albino compounds, polyanion-based compounds.
In a preferred embodiment, the positive electrode active material is a layered transition metal oxide, and the positive electrode active material has a structural formula of Na x MO 2 Wherein M is one or more of transition metal elements Fe, ni, mn, co, cr, 0<x≤1。
In a preferred embodiment, the positive electrode conductive agent includes one or more of carbon nanotubes, conductive carbon black, and graphene, and the negative electrode conductive agent includes one or more of carbon nanotubes, conductive carbon black, and graphene.
In a preferred embodiment, in step S10, the step of preparing the positive electrode slurry includes: taking and uniformly mixing an anode active material, an anode conductive agent and anode binder dry powder; adding a positive electrode solvent and a positive electrode conductive agent into the mixed dry powder to moisten powder particles, slowly stirring, and then stirring at a high speed to obtain moist viscous soft mud-like slurry; and slowly adding the positive electrode solvent/positive electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the positive electrode slurry.
In a preferred embodiment, the positive electrode solvent and the positive electrode conductive agent are added into the mixed dry powder to moisten the powder particles, and the powder particles are slowly stirred and then stirred at a high speed to obtain the moist viscous soft mud-like slurry, wherein the slow stirring speed is 20r/min, the slow stirring time is 30min, the high stirring speed is 25-40r/min, and the high stirring time is 180min.
In a preferred embodiment, the positive electrode binder comprises PVDF and the positive electrode solvent comprises NMP solvent.
In a preferred embodiment, in step S20, the step of preparing the anode slurry includes: taking and uniformly mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder dry powder; adding a negative electrode solvent into the mixed dry powder to moisten powder particles, and stirring at a high speed to obtain moist, viscous and soft mud-like slurry; and slowly adding the negative electrode solvent/negative electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the negative electrode slurry.
In a preferred embodiment, the step of adding a negative electrode solvent to the mixed dry powder to wet the powder particles and stirring at a high speed to obtain a slurry in the form of a wet viscous paste, wherein the stirring speed of the high-speed stirring is 25-40r/min and the stirring time of the high-speed stirring is 120min.
In a preferred embodiment, the negative electrode binder comprises CMC, SBR and the negative electrode solvent comprises NMP solvent.
Compared with the prior art, the preparation method of the sodium battery provided by the invention has the advantages that the adhesive with high cohesiveness and the slurry with excellent conductive network are added to optimize the proportion of active substances, conductive agents and adhesives in the positive and negative electrode slurries, so that the adhesion and conductive performance of the positive and negative electrode materials are improved, the cycle performance of the battery is obviously improved, and the sodium ion battery with excellent performances such as energy density, cycle stability and safety is obtained. The slurry produced by the process has excellent consistency and stability of viscosity, fineness and solid content, and effectively improves the energy density and cycle performance of the battery.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for preparing a sodium battery according to the present invention;
FIG. 2 is a scanning electron microscope image of the positive electrode sheet prepared in example 3 provided by the invention;
fig. 3 is a scanning electron microscope image of the negative electrode plate prepared in example 3 provided by the invention.
[ detailed description ] of the invention
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Please refer to fig. 1, which is a flowchart of a method for preparing a sodium battery according to the present invention. It should be noted that the method of the present invention is not limited to the order of the steps described below, and in other embodiments, the method of the present invention may include only a part of the steps described below, or some of the steps may be deleted.
The preparation method of the sodium battery provided by the invention comprises the following steps:
step S10: preparing positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate; the positive electrode slurry comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder, wherein the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (70-90): 2-5;
step S20: preparing negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to form a negative electrode plate; the negative electrode slurry comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, wherein the mass ratio of the negative electrode active material to the negative electrode conductive agent to the negative electrode binder is (70-90): 2-5;
step S30: and adding a diaphragm between the positive plate and the negative plate for winding, filling the positive plate and the negative plate into a steel shell, and sealing the steel shell after electrolyte is injected to form the sodium battery.
The positive electrode active material comprises any one or more of lamellar transition metal oxide, prussian blue/albino compound and polyanion compound. The positive electrode active material is preferably a layered transition metal oxide, and has a structural general formula of Na x MO 2 Wherein M is one or more of transition metal elements Fe, ni, mn, co, cr, 0<x is less than or equal to 1. The positive electrode conductive agent comprises one or more of carbon nanotubes, conductive carbon black and graphene, preferably a combination of carbon nanotubes and conductive carbon black.
The negative electrode active material comprises one or more of graphite, soft carbon and biomass hard carbon, preferably hard carbon. The negative electrode conductive agent comprises one or more of carbon nanotubes, conductive carbon black and graphene, preferably graphene.
Further, in step S10, the step of preparing the positive electrode slurry includes:
taking and uniformly mixing an anode active material, an anode conductive agent and anode binder dry powder;
adding a positive electrode solvent and a positive electrode conductive agent into the mixed dry powder to moisten powder particles, slowly stirring, and then stirring at a high speed to obtain moist viscous soft mud-like slurry;
and slowly adding the positive electrode solvent/positive electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the positive electrode slurry.
Specifically, the positive electrode solvent and the positive electrode conductive agent are added into the mixed dry powder to moisten powder particles, and the powder particles are slowly stirred and then are stirred at a high speed to obtain moist viscous soft mud-like slurry, wherein the stirring speed of the slow stirring is 20r/min, the stirring time of the slow stirring is 30min, the stirring speed of the high-speed stirring is 25-40r/min, and the stirring time of the high-speed stirring is 180min. The positive electrode binder includes PVDF, and the positive electrode solvent includes an NMP solvent.
As can be appreciated, the preparation of the positive electrode sheet is to mix the positive electrode active material, the conductive agent and the adhesive powder and stir them uniformly; adding a proper amount of solvent to moisten powder particles, dispersing particle aggregates under the action of high-speed shearing force to uniformly distribute the conductive agent, wherein the slurry is in a moist, viscous and soft mud state; after kneading was completed, a solvent was slowly added to adjust the slurry viscosity and solid content to form a black wet and thick liquid, forming a PVDF/NMP oily system. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Further, in step S20, a step of preparing a negative electrode slurry includes:
taking and uniformly mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder dry powder;
adding a negative electrode solvent into the mixed dry powder to moisten powder particles, and stirring at a high speed to obtain moist, viscous and soft mud-like slurry;
and slowly adding the negative electrode solvent/negative electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the negative electrode slurry.
Specifically, adding a negative electrode solvent into the mixed dry powder to moisten powder particles, and stirring at a high speed to obtain moist viscous soft mud-like slurry, wherein the stirring speed of the high-speed stirring is 25-40r/min, and the stirring time of the high-speed stirring is 120min. The negative electrode binder comprises CMC and SBR, and the negative electrode solvent comprises NMP solvent.
As can be appreciated, the preparation of the negative electrode sheet is to mix the negative electrode active material, the conductive agent and the adhesive powder and stir the mixture uniformly; adding a proper amount of solvent to moisten powder particles, dispersing particle aggregates under the action of high-speed shearing force to uniformly distribute the conductive agent, wherein the slurry is in a moist, viscous and soft mud state; after kneading was completed, the viscosity and solids content of the slurry were adjusted by slowly adding a solvent to form a light gray wet, slightly thick liquid to form a hard carbon/CMC/SBR aqueous system. And coating the negative electrode slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
The preparation method of the positive/negative electrode slurry of the sodium ion battery adopts a dry mixing process, also called a kneading process, and the basic process comprises the steps of mixing active substances, conductive agents and dry binder powder, adding a proper amount of solvent for wetting, adding the solvent for high-speed dispersion and crushing, diluting and adjusting the viscosity. When the slurry is stirred at ultrahigh viscosity, the shearing force is large, the conductive agent which is small in particles and easy to agglomerate can be more fully dispersed, meanwhile, the binder is more favorable for dissolution and stabilization, the slurry produced by the process is excellent in viscosity, fineness, solid content consistency and stability, the prepared pole piece is lower in resistivity, and the prepared battery cell is higher in capacity retention rate.
According to the preparation method of the sodium ion battery, the proportion of active substances, the conductive agent and the adhesive in the anode and cathode slurry is optimized, and the adhesive with high adhesion and the slurry with excellent conductive network are added, so that the adhesion and the conductive performance of the anode and cathode materials are improved, and the cycle performance of the battery is obviously improved.
Example 1:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.18g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 1.5g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 30r/min, wetting powder particles, then stirring at high speed to break up and disperse particle aggregates, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 30r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 2:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.22g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 1.7g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 30r/min, wetting powder particles, then stirring at high speed to break up and disperse particle aggregates, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 30r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 3:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.25g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 2g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 30r/min at high speed, wetting powder particles, then stirring at high speed to break up and disperse particle aggregates, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 30r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 4:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.28g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 2.3g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 30r/min, wetting powder particles, then stirring at high speed to break up and disperse particle aggregates, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 30r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 5:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.32g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 2.6g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 30r/min, wetting powder particles, then stirring at high speed to break up and disperse particle aggregates, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 30r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 6:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.25g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing the dry powder; adding 4g of NMP solvent and 2g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 25r/min at high speed, wetting powder particles, crushing and dispersing particle aggregates at high speed, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 25r/min for 120min, crushing and dispersing the particle aggregates, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully mixing uniformly to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 7:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.25g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing; adding 4g of NMP solvent and 2g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 35r/min at high speed, wetting powder particles, crushing and dispersing particle aggregates at high speed, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 35r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Example 8:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.25g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing; adding 4g of NMP solvent and 2g of CNT paste, slowly stirring for 30min at 20r/min, then stirring for 180min at 40r/min at high speed, wetting powder particles, crushing and dispersing particle aggregates at high speed, and regulating viscosity after fully mixing to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, stirring at a high speed of 40r/min for 120min, crushing and dispersing the particle aggregates by stirring at a high speed, finally adding 0.2g of SBR, stirring at 15r/min for 30min, and regulating the viscosity after fully and uniformly mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery. Comparative example 1:
preparing a positive electrode plate: stirring 15g of layered oxide and 0.25g SP,0.3g PVDF dry powder for 30min at a stirring speed of 15r/min, and uniformly mixing; adding 4g of NMP solvent and 2g of CNT paste, slowly stirring for 210min at 20r/min, crushing and dispersing the particle agglomeration, and fully and uniformly mixing to adjust the viscosity to obtain the anode paste. And coating the positive electrode slurry on an aluminum foil, and rolling and forming to obtain the positive electrode plate.
Preparing a negative electrode plate: adding 15g of hard carbon, 12g of CMC glue solution with the concentration of 1.7 percent and 0.4g of graphene, slowly stirring for 120min at the stirring speed of 20r/min, and uniformly mixing; adding 2g of NMP solvent, slowly stirring for 120min at 20r/min, crushing and dispersing the particle aggregates, finally adding 0.2g of SBR, stirring for 30min at 15r/min, and regulating the viscosity after fully mixing to obtain the negative electrode slurry. Coating the slurry on an aluminum foil, and rolling and forming to obtain the negative electrode plate.
Dividing the formed positive and negative electrode plates into a positive electrode roll and a negative electrode roll, welding tabs on the positive electrode roll, adding a diaphragm between the positive and negative electrode plates for winding, and assembling into a steel shell.
Baking the assembled battery cell, injecting electrolyte, and sealing. And (5) performing chemical composition on the finished battery.
Referring to examples 1-8 provided by the invention, specifically, the positive electrode conductive agents SP and CNT added in the steps of preparing the positive electrode sheet in examples 1-5 are different, and the rest steps are the same, so as to explore the influence of the conductive agent content on the performance of the sodium battery; in the steps of preparing the positive plate and the negative plate in the embodiment 3 and the embodiment 6-8, the stirring speeds of high-speed stirring are different, and the other steps are the same, so that the influence of the stirring mode on the performance of the sodium battery is explored.
The sodium batteries prepared in examples 1 to 5 were subjected to performance test to obtain the following table 1:
TABLE 1
As can be seen from Table 1, referring to examples 1-5, the sodium ion battery prepared by the invention has a capacity retention rate of more than 80% after 600 cycles, and has excellent properties. Specifically, as can be seen from comparison of examples 1-3, the conductive agent has the function of providing a channel for electron movement in the electrode, reducing the contact resistance of the electrode, improving the electron conductivity, promoting the infiltration of the electrolyte to the electrode sheet, effectively improving the migration rate of sodium ions in the electrode material, and reducing the polarization, thereby improving the charge and discharge efficiency of the electrode and the service life of the sodium battery. As can be seen from the comparison of examples 3 to 5, too high a content of the conductive agent reduces the relative content of the active material, resulting in a reduction in battery capacity. Meanwhile, the content of the conductive agent is too high, so that the difficulty in dispersing ingredients is increased, if the dispersing effect is not achieved, the conductive agent is agglomerated, electrolyte is concentrated on one pole with high content of the conductive agent, the lithium ion transmission process of the other pole is slow, the polarization degree is high, and the battery is easy to lose efficacy after repeated circulation, so that the overall performance of the battery is affected.
Therefore, when the content of the conductive agent is too low, the conductive substance cannot constitute an effective conductive network, resulting in an increase in the internal resistance of the battery. When the content of the conductive agent is too high, more and more conductive agent builds an effective conductive network, and the conductivity is not increased significantly after the threshold value is reached. Therefore, the content of the conductive agent reaches an optimal point (example 3), and too high a content of the conductive agent reduces the electrode density, so that the capacity is reduced; while too low a content results in low utilization of active materials in the electrode and reduced high-rate discharge performance. The content of the conductive agent is proper, so that higher discharge capacity and better cycle performance can be obtained.
The sodium batteries prepared in example 3, examples 6 to 8 and comparative example 1 were subjected to performance tests, resulting in the following table 2:
TABLE 2
As can be seen from Table 2, referring to example 3 and examples 6-8, the capacity retention rate of the sodium ion battery prepared by the invention after 600 cycles can reach more than 80%, and the sodium ion battery has excellent properties. Specifically, as can be seen from comparison of examples 6 and 3 with comparative example 1, when the positive and negative electrode slurries are stirred slowly, the dispersion of the conductive agent is uneven, the electrolyte is concentrated in the electrode with high conductive agent content, and the lithium ion transmission process of the other electrode is slow, and the electrolyte is easy to lose effectiveness after repeated circulation, thereby affecting the overall performance of the battery. When the positive and negative electrode slurry is stirred with ultrahigh viscosity, the conductive agent with fine particles and easy agglomeration can be fully dispersed by large shearing force, meanwhile, the binder is more favorable for dissolution and stability, the slurry viscosity, fineness and solid content consistency and stability are more excellent, the prepared pole piece has lower resistivity, the prepared battery cell has higher capacity retention rate, and the battery has stronger cyclical stability and better battery performance. As can be obtained by comparison of examples 3, 7, 8 and comparative example 1, if the stirring intensity of the positive and negative electrode slurry is too high, the conductive agent is crushed into fine particles, and although the contact and dispersion effect between the conductive agent and the active material is increased, the long-distance conductive performance of the conductive agent network is deteriorated, and the resistance of the prepared electrode sheet is increased, and the corresponding battery performance is deteriorated instead. Therefore, as the stirring strength of the positive and negative electrode slurry increases, the resistance of the electrode sheet tends to decrease and then increase, and the multiplying power and the cycle performance of the battery also become better and then correspondingly worse, and the stirring strength in example 3 is the best and the performance is the most excellent.
Fig. 2 is a scanning electron microscope image of the positive electrode plate prepared in example 3 provided by the present invention, and fig. 3 is a scanning electron microscope image of the negative electrode plate prepared in example 3 provided by the present invention, and it can be seen from fig. 2 and fig. 3 that the positive electrode plate and the negative electrode plate prepared in example 2 of the present invention have good morphology, and the performance of the sodium battery is excellent.
In summary, according to the preparation method of the sodium battery provided by the invention, the active substances, the conductive agent and the adhesive in the positive and negative electrode slurry are optimized by adding the adhesive with high cohesiveness and the slurry with excellent conductive network, so that the adhesion and the conductive performance of the positive and negative electrode materials are improved, the cycle performance of the battery is obviously improved, and the sodium ion battery with excellent performances such as energy density, cycle stability and safety is obtained. The slurry produced by the process has excellent consistency and stability of viscosity, fineness and solid content, and effectively improves the energy density and cycle performance of the battery.
The foregoing description is only of embodiments of the present invention, and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes using the descriptions and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for preparing a sodium battery, comprising the steps of:
step S10: preparing positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate; the positive electrode slurry comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder, wherein the mass ratio of the positive electrode active material to the positive electrode conductive agent to the positive electrode binder is (70-90): 2-5;
step S20: preparing negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to form a negative electrode plate; the negative electrode slurry comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, wherein the mass ratio of the negative electrode active material to the negative electrode conductive agent to the negative electrode binder is (70-90): 2-5;
step S30: and adding a diaphragm between the positive plate and the negative plate for winding, filling the positive plate and the negative plate into a steel shell, and sealing the steel shell after electrolyte is injected to form the sodium battery.
2. The method of manufacturing a sodium battery according to claim 1, wherein the positive electrode active material comprises any one or more of layered transition metal oxides, prussian blue/whitening compounds, and polyanion-based compounds.
3. The method for preparing a sodium battery according to claim 1, wherein the positive electrode active material is a layered transition metal oxide, and the positive electrode active material has a general structural formula of Na x MO 2 Wherein M is one or more of transition metal elements Fe, ni, mn, co, cr, 0<x≤1。
4. The method for preparing a sodium battery according to claim 1, wherein the positive electrode conductive agent comprises one or more of carbon nanotubes, conductive carbon black and graphene, and the negative electrode conductive agent comprises one or more of carbon nanotubes, conductive carbon black and graphene.
5. The method of manufacturing a sodium battery according to claim 1, wherein in step S10, the step of manufacturing the positive electrode slurry includes:
taking and uniformly mixing an anode active material, an anode conductive agent and anode binder dry powder;
adding a positive electrode solvent and a positive electrode conductive agent into the mixed dry powder to moisten powder particles, slowly stirring, and then stirring at a high speed to obtain moist viscous soft mud-like slurry;
and slowly adding the positive electrode solvent/positive electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the positive electrode slurry.
6. The method of manufacturing a sodium battery according to claim 5, wherein the step of adding a positive electrode solvent and a positive electrode conductive agent to the mixed dry powder to wet the powder particles, slowly stirring the wet slurry, and then stirring the wet slurry at a high speed to obtain a wet viscous paste, wherein the slow stirring speed is 20r/min, the slow stirring time is 30min, the stirring speed of the high speed stirring is 25-40r/min, and the stirring time of the high speed stirring is 180min.
7. The method of manufacturing a sodium battery according to claim 5, wherein the positive electrode binder comprises PVDF and the positive electrode solvent comprises an NMP solvent.
8. The method of manufacturing a sodium battery according to claim 1, wherein in step S20, the step of manufacturing the negative electrode slurry includes:
taking and uniformly mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder dry powder;
adding a negative electrode solvent into the mixed dry powder to moisten powder particles, and stirring at a high speed to obtain moist, viscous and soft mud-like slurry;
and slowly adding the negative electrode solvent/negative electrode binder into the wet thick and soft mud-like slurry to adjust the viscosity and solid content of the slurry, and stirring to obtain the negative electrode slurry.
9. The method of producing a sodium battery according to claim 8, wherein in the step of adding a negative electrode solvent to the mixed dry powder to wet the powder particles and stirring at a high speed to obtain a wet viscous paste-like slurry, the stirring speed of the high-speed stirring is 25 to 40r/min and the stirring time of the high-speed stirring is 120min.
10. The method of manufacturing a sodium battery according to claim 8, wherein the negative electrode binder comprises CMC, SBR, and the negative electrode solvent comprises NMP solvent.
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