CN116230854A - Negative electrode plate of sodium ion battery, preparation method of negative electrode plate and sodium ion battery - Google Patents
Negative electrode plate of sodium ion battery, preparation method of negative electrode plate and sodium ion battery Download PDFInfo
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- CN116230854A CN116230854A CN202310257526.7A CN202310257526A CN116230854A CN 116230854 A CN116230854 A CN 116230854A CN 202310257526 A CN202310257526 A CN 202310257526A CN 116230854 A CN116230854 A CN 116230854A
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- ion battery
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 81
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002562 thickening agent Substances 0.000 claims abstract description 44
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 239000006258 conductive agent Substances 0.000 claims abstract description 30
- 238000006467 substitution reaction Methods 0.000 claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 38
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 38
- 239000011267 electrode slurry Substances 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 239000002174 Styrene-butadiene Substances 0.000 claims description 13
- 229910021385 hard carbon Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910021384 soft carbon Inorganic materials 0.000 claims description 7
- 239000006256 anode slurry Substances 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 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 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229940105329 carboxymethylcellulose Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 230000009469 supplementation Effects 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229940091252 sodium supplement Drugs 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- Secondary Cells (AREA)
Abstract
The present disclosure provides a negative electrode piece of a sodium ion battery, comprising a negative electrode material, a binder, a conductive agent, a thickener and a current collector, wherein the substitution degree of the thickener ranges from 0.9 to 1.4. The disclosure also provides a preparation method of the negative electrode piece of the sodium ion battery and the sodium ion battery.
Description
Technical Field
The disclosure relates to the technical field of sodium ion batteries, in particular to a negative electrode plate of a sodium ion battery, a preparation method of the negative electrode plate of the sodium ion battery and the sodium ion battery.
Background
At present, with the development of new energy industry, lithium ion battery technology is also rapidly advancing, however, the shortage of lithium resources causes the continuous increase of lithium battery cost, which hinders the application of lithium element in the energy storage field. Therefore, there is a need to develop and design new energy storage devices to achieve partial replacement of lithium ion batteries.
The sodium element and the lithium element are positioned in the same main group, have similar chemical properties, and have excellent energy storage performance as electrode materials. Meanwhile, sodium metal resources are abundant in earth and far larger than lithium metal, so that research and development of the sodium ion battery energy storage device have natural advantages in order to meet huge market demands.
In the field of energy storage devices, the energy density, the charge-discharge multiplying power, the cost, the circulation and other electrochemical performances are used as evaluation criteria to evaluate the energy storage material. Since the relative atomic mass of sodium is higher than that of lithium, the theoretical energy density of sodium ion batteries is lower compared to lithium ion batteries.
Sodium supplementation for sodium ion batteries is a solution to improve the energy density and charge-discharge rate performance of sodium ion batteries. Sodium supplementation of sodium ion batteries is divided into negative electrode sodium supplementation and positive electrode sodium supplementation, wherein the negative electrode sodium supplementation comprises an electrochemical pre-sodium treatment method, a negative electrode sodium supplementation additive sodium powder method and the like; the positive electrode sodium supplement is to add sodium-rich substances into the positive electrode, and the electrochemical reaction is carried out to release sodium by utilizing the higher voltage of the positive electrode when the battery is charged and discharged. However, the above solution for supplementing sodium to a sodium ion battery may have an adverse effect on the performance of the sodium ion battery, and the process is complex, so that commercialization is difficult.
Therefore, how to effectively improve the performance of the sodium ion battery through simple procedures is a problem to be solved.
Disclosure of Invention
The embodiment of the disclosure provides a negative electrode plate of a sodium ion battery, a preparation method of the negative electrode plate of the sodium ion battery and the sodium ion battery.
In a first aspect, embodiments of the present disclosure provide a negative electrode tab of a sodium ion battery, including a negative electrode material, a binder, a conductive agent, a thickener, and a current collector, where the thickener has a substitution degree ranging from 0.9 to 1.4.
In some embodiments, the thickener comprises carboxymethyl cellulose CMC.
In some embodiments, the ratio of the parts by weight of the negative electrode material, the binder, the conductive agent, and the thickener in the negative electrode sheet is (80 to 98): (0.1 to 5).
In some embodiments, the negative electrode material includes any one of hard carbon, soft carbon, and metal converted matter, the binder includes any one of styrene-butadiene rubber SBR, and polyacrylic acid PAA, and the conductive agent includes any one of conductive carbon black SP, carbon nanotube CNT, and graphene.
In a second aspect, an embodiment of the present disclosure provides a method for preparing a negative electrode plate of a sodium ion battery, where the method includes:
uniformly stirring and dispersing a negative electrode material, a binder, a conductive agent and a thickening agent to obtain a negative electrode slurry, wherein the substitution degree of the thickening agent ranges from 0.9 to 1.4;
and coating the negative electrode slurry on a current collector, and baking and rolling to obtain a negative electrode plate.
In some embodiments, the thickener comprises carboxymethyl cellulose CMC.
In some embodiments, the anode material, the binder, the conductive agent and the thickener are uniformly stirred and dispersed to obtain anode slurry, which comprises:
and uniformly stirring and dispersing the anode material, the binder, the conductive agent and the thickener according to the weight ratio of (80-98), 0.1-5 and 0.1-5 to obtain the anode slurry.
In some embodiments, the negative electrode material includes any one of hard carbon, soft carbon, and metal converted matter, the binder includes any one of styrene-butadiene rubber SBR, and polyacrylic acid PAA, and the conductive agent includes any one of conductive carbon black SP, carbon nanotube CNT, and graphene.
In a third aspect, embodiments of the present disclosure provide a sodium ion battery comprising the negative electrode tab of the first aspect of embodiments of the present disclosure.
In a fourth aspect, embodiments of the present disclosure provide a sodium ion battery including a negative electrode tab prepared according to the preparation method of the second aspect of embodiments of the present disclosure.
In the embodiment of the disclosure, in the negative electrode plate of the sodium ion battery, the substitution degree of the thickener ranges from 0.9 to 1.4, so that poor heat collection stability of the CMC (sodium-alkali resistance) caused by non-uniform substitution can be avoided, the influence of overhigh viscosity of the negative electrode slurry on the processing performance of the negative electrode slurry can be avoided, and the removed sodium ion can play a role in supplementing sodium by adopting the thickener ranging from 0.9 to 1.4, thereby being beneficial to improving the energy density and the charge-discharge rate performance of the sodium ion battery.
Drawings
FIG. 1 is a flow chart of a method of making a negative electrode tab for a sodium ion battery in an embodiment of the disclosure;
fig. 2 is a schematic diagram of the capacity retention of a sodium ion battery in an embodiment of the present disclosure.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present disclosure, the negative electrode piece of the sodium ion battery, the preparation method of the negative electrode piece of the sodium ion battery and the sodium ion battery provided by the present disclosure are described in detail below with reference to the accompanying drawings.
Example embodiments will be described more fully hereinafter with reference to the accompanying drawings, but may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Embodiments of the disclosure and features of embodiments may be combined with each other without conflict.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In a first aspect, an embodiment of the present disclosure provides a negative electrode tab of a sodium ion battery, including a negative electrode material, a binder, a conductive agent, a thickener, and a current collector, where the thickener has a substitution degree ranging from 0.9 to 1.4.
The anode material is not particularly limited in the embodiment of the present disclosure. For example, the anode material includes any one of hard carbon, soft carbon, and metal conversion products.
The binder is not particularly limited in the embodiments of the present disclosure. In some embodiments, the binder includes an organic binder such as styrene butadiene rubber (SBR, polymer ized Styrene Butadiene Rubber), polyacrylic acid (PAA, poly Acrylic Acid), and the like. For example, the binder includes one or a mixture of several of PAA, polytetrafluoroethylene (PTFE), polypropylene alcohol (PVA, polyvinyl Alcohol), sodium Alginate (Alg, sodium Alginate), SBR.
The embodiment of the present disclosure is not particularly limited to the conductive agent. For example, the conductive agent includes any one of conductive Carbon black SP, carbon Nanotubes (CNT), and graphene.
The thickener is not particularly limited in the embodiments of the present disclosure. For example, the thickener includes: carboxymethyl cellulose (CMC, carboxy Methyl Cellulose).
The explanation will be made taking a thickener as CMC.
CMC is also one of aqueous binders, and is widely used in negative electrodes of lithium ion batteries. In the embodiments of the present disclosure, since the sodium ion battery is different from the lithium ion battery, the CMC in the negative electrode tab of the sodium ion battery needs to be modified.
The inventors of the present disclosure studied and found that in lithium ion batteries, the degree of substitution of CMC generally ranges from 0.65 to 0.8; if the substitution degree of CMC is too low, the CMC is easy to be substituted unevenly, so that the CMC has poor acid-base resistance and thermal stability; if the CMC is substituted by the degree passageway, the viscosity of the negative electrode slurry is too high, and part of sodium ions in the lithium ion battery are separated, so that the overall electrical performance of the battery core of the lithium ion battery is reduced.
The inventor of the present disclosure further researches and found that, in the sodium ion battery, CMC with high substitution degree is adopted, and even if sodium ions are extracted, the electrical performance of the whole battery cell of the sodium ion battery is not adversely affected; and the released sodium ions can play a role in supplementing sodium, so that the energy density and the charge-discharge rate performance of the sodium ion battery are improved.
The embodiment of the present disclosure does not particularly limit the substitution degree of CMC in the sodium ion battery. For example, the degree of substitution of CMC is any one of 1.1, 1.2, and 0.9.
In the negative electrode plate of the sodium ion battery provided by the embodiment of the disclosure, the substitution degree range of the thickener is 0.9 to 1.4, so that poor heat collection stability of the CMC (sodium-alkali resistance) caused by non-uniform substitution can be avoided, the influence of overhigh viscosity of the negative electrode slurry on the processing performance of the negative electrode slurry can be avoided, and the thickener in the range of 0.9 to 1.4 is adopted, so that the removed sodium ion can play a role in supplementing sodium, and the energy density and the charge-discharge rate performance of the sodium ion battery are improved.
In some embodiments, the thickener comprises carboxymethyl cellulose CMC.
The embodiment of the disclosure does not limit the proportion of the negative electrode material, the binder, the conductive agent and the thickener in parts by weight in the negative electrode plate in particular.
In some embodiments, the ratio of the parts by weight of the negative electrode material, the binder, the conductive agent, and the thickener in the negative electrode sheet is (80 to 98): (0.1 to 5).
In some embodiments, the ratio of parts by weight of the negative electrode material, binder, conductive agent, and thickener is 90.0:4.0:4.5:1.5.
The embodiment of the present disclosure does not particularly limit the negative electrode material, the binder, the conductive agent, and the thickener.
In some embodiments, the negative electrode material includes any one of hard carbon, soft carbon, metal conversion, the binder includes an organic binder such as SBR, PAA, etc., and the conductive agent includes conductive carbon black SP, CNT, graphene, etc.
In a second aspect, referring to fig. 1, an embodiment of the present disclosure provides a method for preparing a negative electrode tab of a sodium ion battery, the method comprising:
s1, uniformly stirring and dispersing a negative electrode material, a binder, a conductive agent and a thickening agent to obtain negative electrode slurry, wherein the substitution degree of the thickening agent ranges from 0.9 to 1.4;
s2, coating the negative electrode slurry on a current collector, and baking and rolling to obtain a negative electrode plate.
In the embodiment of the disclosure, when the negative electrode plate of the sodium ion battery is prepared, the thickener with the substitution degree ranging from 0.9 to 1.4 is adopted, so that poor heat collection stability of the CMC (sodium-alkali resistance) caused by non-uniform substitution can be avoided, the influence of the too high viscosity of the negative electrode slurry on the processing performance of the negative electrode slurry can be avoided, and the thickener with the substitution degree ranging from 0.9 to 1.4 is adopted, so that the removed sodium ion can play a role in supplementing sodium, and the energy density and the charge-discharge rate performance of the sodium ion battery are improved.
In some embodiments, the thickener comprises carboxymethyl cellulose CMC.
In the embodiment of the disclosure, when the negative electrode piece of the sodium ion battery is prepared, the proportion of the negative electrode material, the binder, the conductive agent and the thickener in parts by weight is not particularly limited.
In some embodiments, the anode material, the binder, the conductive agent and the thickener are uniformly stirred and dispersed to obtain anode slurry, which comprises:
and uniformly stirring and dispersing the anode material, the binder, the conductive agent and the thickener according to the weight ratio of (80-98), 0.1-5 and 0.1-5 to obtain the anode slurry.
In some embodiments, the ratio of parts by weight of the negative electrode material, binder, conductive agent, and thickener is 90.0:4.0:4.5:1.5.
The embodiment of the disclosure does not limit the negative electrode material, the binder, the conductive agent and the thickener for preparing the negative electrode plate of the sodium ion battery in particular.
In some embodiments, the negative electrode material includes any one of hard carbon, soft carbon, metal conversion, the binder includes an organic binder such as SBR, PAA, etc., and the conductive agent includes conductive carbon black SP, CNT, graphene, etc.
In the embodiment of the disclosure, after the negative electrode piece is prepared through steps S1 to S2, the negative electrode piece, the diaphragm and the positive electrode piece are assembled into the battery cell through a winding mode, and then the sodium ion battery is prepared through the procedures of top sealing, liquid injection (sodium salt concentration is 1 mol/L), standing, formation, shaping, degassing and the like.
In a third aspect, embodiments of the present disclosure provide a sodium ion battery comprising the negative electrode tab of the first aspect of embodiments of the present disclosure.
In a fourth aspect, embodiments of the present disclosure provide a sodium ion battery including a negative electrode tab prepared according to the preparation method of the second aspect of embodiments of the present disclosure.
In order to enable those skilled in the art to more clearly understand the technical solutions provided by the embodiments of the present disclosure, the following details of the technical solutions provided by the embodiments of the present disclosure are described by specific embodiments:
example 1
Hard carbon negative electrode, SBR, SP, CMC with substitution degree of 1.1 were mixed in a ratio of 90.0:4.0:4.5:1.5, uniformly stirring and dispersing to obtain negative electrode slurry; then coating and rolling to obtain a negative electrode plate; and then the negative electrode plate, the diaphragm and the positive electrode plate are assembled into a battery core in a winding way, and the sodium ion battery is prepared through the procedures of top sealing, liquid injection (the concentration of sodium salt is 1 mol/L), standing, formation, shaping, degassing and the like.
The viscosity of the negative electrode slurry obtained in this example, the first effect of the sodium ion battery, and the cycle performance are shown in table 1; the capacity retention rate of the sodium ion battery obtained in this example is shown in fig. 2 in a charge 1C/discharge 10C scenario.
Example 2
Hard carbon negative electrode, SBR, SP, CMC with substitution degree of 1.2 were mixed in a ratio of 90.0:4.0:4.5:1.5, uniformly stirring and dispersing to obtain negative electrode slurry; then coating and rolling to obtain a negative electrode plate; and then the negative electrode plate, the diaphragm and the positive electrode plate are assembled into a battery cell in a winding way, and the sodium ion battery is prepared through the procedures of top sealing, liquid injection (sodium salt concentration is 1 mol/L), standing, formation, shaping, degassing and the like.
The viscosity of the negative electrode slurry obtained in this example, the first effect of the sodium ion battery, and the cycle performance are shown in table 1; the capacity retention rate of the sodium ion battery obtained in this example is shown in fig. 2 in a charge 1C/discharge 10C scenario.
Example 3
Hard carbon negative electrode, SBR, SP, CMC with substitution degree of 0.9, in a ratio of 90.0:4.0:4.5:1.5, uniformly stirring and dispersing to obtain negative electrode slurry; then coating and rolling to obtain a negative electrode plate; and then the negative electrode plate, the diaphragm and the positive electrode plate are assembled into a battery cell in a winding way, and the sodium ion battery is prepared through the procedures of top sealing, liquid injection (sodium salt concentration is 1 mol/L), standing, formation, shaping, degassing and the like.
The viscosity of the negative electrode slurry obtained in this example, the first effect of the sodium ion battery, and the cycle performance are shown in table 1; the capacity retention rate of the sodium ion battery obtained in this example is shown in fig. 2 in a charge 1C/discharge 10C scenario.
Comparative example 1
Hard carbon negative electrode, SBR, SP, CMC with substitution degree of 0.7, in a ratio of 90.0:4.0:4.5:1.5, uniformly stirring and dispersing to obtain negative electrode slurry; then coating and rolling to obtain a negative electrode plate; and then the negative electrode plate, the diaphragm and the positive electrode plate are assembled into a battery cell in a winding way, and the sodium ion battery is prepared through the procedures of top sealing, liquid injection (sodium salt concentration is 1 mol/L), standing, formation, shaping, degassing and the like.
The viscosity of the negative electrode slurry obtained in this comparative example, the first effect of the sodium ion battery, and the cycle performance are shown in table 1; the capacity retention rate of the sodium ion battery obtained in this comparative example is shown in fig. 2 in a charge 1C/discharge 10C scenario.
Comparative example 2
Hard carbon negative electrode, SBR, SP, CMC with substitution degree of 1.6 were mixed in a ratio of 90.0:4.0:4.5:1.5, uniformly stirring and dispersing to obtain negative electrode slurry; then coating and rolling to obtain a negative electrode plate; and then the negative electrode plate, the diaphragm and the positive electrode plate are assembled into a battery cell in a winding way, and the sodium ion battery is prepared through the procedures of top sealing, liquid injection (sodium salt concentration is 1 mol/L), standing, formation, shaping, degassing and the like.
The viscosity of the negative electrode slurry obtained in this comparative example, the first effect of the sodium ion battery, and the cycle performance are shown in table 1; the capacity retention rate of the sodium ion battery obtained in this comparative example is shown in fig. 2 in a charge 1C/discharge 10C scenario.
TABLE 1
Degree of substitution | Viscosity (mPas) | First effect (%) | Cycle performance (100 cyc) |
1.1 | 8300 | 84.7 | 95.6 |
1.2 | 12500 | 85.2 | 95.3 |
0.9 | 7500 | 83.4 | 95.2 |
0.7 | 7200 | 81.5 | 93.7 |
1.6 | 28000 | / | / |
As shown in table 1 and fig. 2, the substitution degree was in the range of 0.9 to 1.4, and the substitution degree of CMC was increased, so that the initial efficiency, cycle performance, and charge-discharge rate performance of the sodium ion battery were improved. The reason is that the CMC may ionize part of sodium ions during charging and discharging, and the movement of the sodium ions on the CMC surface increases the diffusion rate of the sodium ions on the negative electrode plate, so as to significantly increase the rate capability of the battery cell, and the ionized sodium ions also play a role in supplementing the consumption of the negative electrode solid electrolyte interface (SEI, solid Electrolyte Interface) film, so as to increase the initial effect and the cycle performance of the sodium ion battery cell.
As shown in table 1 and fig. 2, if the substitution degree of CMC exceeds the range of 0.9 to 1.4 to reach 1.6 or more, the viscosity of the negative electrode slurry is significantly increased, thereby affecting the processability of the negative electrode slurry.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and should be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, it will be apparent to one skilled in the art that features, characteristics, and/or elements described in connection with a particular embodiment may be used alone or in combination with other embodiments unless explicitly stated otherwise. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the disclosure as set forth in the appended claims.
Claims (10)
1. The negative electrode plate of the sodium ion battery comprises a negative electrode material, a binder, a conductive agent, a thickener and a current collector, and is characterized in that the substitution degree of the thickener ranges from 0.9 to 1.4.
2. The negative electrode tab of claim 1, wherein the thickener comprises carboxymethyl cellulose CMC.
3. The negative electrode sheet according to claim 1 or 2, wherein the ratio of parts by weight of the negative electrode material, the binder, the conductive agent, and the thickener in the negative electrode sheet is (80 to 98): (0.1 to 5).
4. The negative electrode sheet according to claim 3, wherein the negative electrode material comprises any one of hard carbon, soft carbon, and metal converted matter, the binder comprises at least one of styrene-butadiene rubber SBR, and polyacrylic acid PAA, and the conductive agent comprises any one of conductive carbon black SP, carbon nanotube CNT, and graphene.
5. The preparation method of the sodium ion battery negative electrode plate is characterized by comprising the following steps:
uniformly stirring and dispersing a negative electrode material, a binder, a conductive agent and a thickening agent to obtain a negative electrode slurry, wherein the substitution degree of the thickening agent ranges from 0.9 to 1.4;
and coating the negative electrode slurry on a current collector, and baking and rolling to obtain a negative electrode plate.
6. The method of claim 5, wherein the thickener comprises carboxymethyl cellulose CMC.
7. The method according to claim 5 or 6, wherein the anode material, the binder, the conductive agent, and the thickener are uniformly stirred and dispersed to obtain an anode slurry, comprising:
and uniformly stirring and dispersing the anode material, the binder, the conductive agent and the thickener according to the weight ratio of (80-98), 0.1-5 and 0.1-5 to obtain the anode slurry.
8. The method according to claim 7, wherein the negative electrode material comprises any one of hard carbon, soft carbon, and metal converted matter, the binder comprises any one of styrene-butadiene rubber SBR, and polyacrylic acid PAA, and the conductive agent comprises any one of conductive carbon black SP, carbon nanotube CNT, and graphene.
9. A sodium ion battery characterized in that it comprises a negative electrode sheet according to any one of claims 1 to 4.
10. A sodium ion battery, characterized in that it comprises a negative electrode sheet prepared according to the preparation method of any one of claims 5 to 8.
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CN116646526A (en) * | 2023-07-25 | 2023-08-25 | 中国华能集团清洁能源技术研究院有限公司 | Positive electrode interface film of sodium ion battery, preparation method of positive electrode interface film and sodium ion battery |
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CN116646526B (en) * | 2023-07-25 | 2023-10-20 | 中国华能集团清洁能源技术研究院有限公司 | Positive electrode interface film of sodium ion battery, preparation method of positive electrode interface film and sodium ion battery |
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