CN114520311A - Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery - Google Patents
Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery Download PDFInfo
- Publication number
- CN114520311A CN114520311A CN202210116601.3A CN202210116601A CN114520311A CN 114520311 A CN114520311 A CN 114520311A CN 202210116601 A CN202210116601 A CN 202210116601A CN 114520311 A CN114520311 A CN 114520311A
- Authority
- CN
- China
- Prior art keywords
- sodium
- ion battery
- pole piece
- negative pole
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 46
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004744 fabric Substances 0.000 claims abstract description 48
- 239000006258 conductive agent Substances 0.000 claims abstract description 34
- 239000002346 layers by function Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 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 claims description 20
- -1 polypropylene Polymers 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 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 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- KRKSIZNDZZMANM-UHFFFAOYSA-N sodium cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Na+] KRKSIZNDZZMANM-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 2
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RMZMFASTOVOJPY-UHFFFAOYSA-N [Fe].[Mn].[Ni].[Na] Chemical compound [Fe].[Mn].[Ni].[Na] RMZMFASTOVOJPY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LEBYISUPSSNHTJ-UHFFFAOYSA-N methoxy-methyl-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound COS(C)(=O)=S LEBYISUPSSNHTJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a negative pole piece for a sodium ion battery, a preparation method of the negative pole piece and the sodium ion battery. The preparation method of the negative pole piece for the sodium ion battery comprises the following steps: 1) preparing a melt-blown fabric, and loading a conductive agent on the melt-blown fabric to obtain the melt-blown fabric containing the conductive agent; 2) soaking the melt-blown fabric containing the conductive agent in hydrofluoric acid solution, washing with water, and drying to obtain a functional layer; 3) and carrying out thermal bonding according to the sequence of one functional layer, one intermediate structural layer and the other functional layer. The negative pole piece for the sodium ion battery provided by the invention can effectively inhibit dendrites formed by sodium metal in the circulation process, and improve the circulation performance and safety performance of the battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a negative pole piece for a sodium ion battery, a preparation method of the negative pole piece and the sodium ion battery.
Background
In the 21 st century, lithium batteries are used in a variety of fields such as mobile phones, computers, wearable devices, electric automobiles, two-wheel bicycles, electric tools, street lamps and the like. With the increasing use amount of lithium batteries, the consumption of lithium resources shows the phenomena that the use amount is increasing and the consumption speed is high, and the increase of the production amount of lithium cannot meet the increase of the consumption amount, because the lithium resources are limited and mainly exist in the states of spodumene ores and salt lake lithium, and the salt lake lithium cannot be extracted in winter, so that the prices of lithium metal and compounds rise this year.
In contrast, sodium is widely available and abundant, and the storage capacity of sodium is 420 times of that of lithium, and the price is far lower than that of lithium. In recent years, with the drastic increase of lithium price, the sodium-ion battery is expected to be 30-50% lower in cost than the lithium-ion battery and is widely concerned, and particularly has attractive application prospects in the fields of energy storage, hybrid power and lead-acid battery replacement.
However, the positive electrode materials of the sodium ion battery mainly comprise Prussian blue, sodium vanadium phosphate and sodium iron nickel manganese, the gram capacity is between 100 and 160mAh, the negative electrode materials generally adopt hard carbon, and the gram capacity is between 200 and 280mAh, so that the gram capacity of the positive electrode and the negative electrode of the sodium ion battery is lower, and therefore the energy density of the sodium ion battery is always different from that of the lithium ion battery.
Under the condition that gram capacity of the anode material and the cathode material is not effectively improved, sodium metal (with theoretical specific capacity 1166mAh/g) is used as the cathode to become an effective choice for improving energy density of the battery, but the sodium metal is easy to generate defects such as dendrites and the like in the charging process, and safety performance of the battery is affected.
Disclosure of Invention
In order to solve the technical problems, the invention provides a negative pole piece for a sodium-ion battery, a preparation method of the negative pole piece and the sodium-ion battery.
In a first aspect, the preparation method of the negative electrode plate provided by the invention comprises the following steps:
1) preparing a melt-blown fabric, and loading a conductive agent on the melt-blown fabric to obtain the melt-blown fabric containing the conductive agent;
2) soaking the melt-blown fabric containing the conductive agent in hydrofluoric acid solution, washing with water, and drying to obtain a functional layer;
3) thermal bonding is performed in the order of one of the functional layers, one of the intermediate structural layers and the other of the functional layers.
According to the invention, the surface of the negative pole piece is free of the negative active material, so that the metal sodium is more uniformly deposited on the surface of the negative pole piece and in the internal pores when the negative pole piece is charged for the first time, and the porous conductive fibers are sprayed on the upper layer and the lower layer of the negative pole in a melting way, so that the overpotential of the metal sodium deposition can be effectively reduced, the generation of sodium dendrite is inhibited, and the cycle performance of the battery is improved.
Preferably, in the step 1), the thickness of the melt-blown fabric is 1-20 μm, and the porosity is 40-80%.
Further preferably, in step 1), the conductive agent is selected from one or more of carbon black, acetylene black, carbon fiber and carbon nanotube, and preferably carbon black or acetylene black.
Further preferably, in the step 1), the loading amount of the conductive agent is 10-60%.
According to the invention, by adopting the materials and parameters of the functional layer, the overpotential of metal sodium deposition can be further reduced, the generation of sodium dendrites is inhibited, and the cycle life of the battery is prolonged.
Preferably, in the step 2), the steel plate is soaked in a 5-10% hydrofluoric acid solution for 5-10 hours.
In the invention, hydrofluoric acid with specific concentration is adopted for soaking for a certain time, so that the melt-blown cloth fiber contains F ion activation points, and the absorption of subsequent electrolyte and the uniform deposition of sodium ions in the subsequent charging process are facilitated.
In order to further improve the first discharge capacity, safety and cycle life of the sodium-ion battery prepared by the invention. The invention optimizes the concrete process and parameters as follows:
further preferably, in the step 2), the washing with deionized water is performed until the washing with deionized water is neutral.
Preferably, in the step 2), the drying is performed for 4-10 hours at 70-90 ℃ in vacuum.
In the invention, under the washing and drying conditions in the step 2), the functional layer with excellent performance can be prepared better, and meanwhile, the temperature is lower than the melting temperature of the melt-blown fabric, so that the structure of the melt-blown fabric is not damaged.
Preferably, in the step 3), the temperature of the thermal bonding is 50-120 ℃.
Further preferably, in the step 3), the pressure of the thermal bonding is 0.5 to 10 MPa.
In the invention, the optimized parameters of the thermal bonding are further adopted, so that the effective combination of the functional layer and the structural layer is ensured, the layers are ensured to play a role, and the performance of the prepared negative pole piece is better.
In the step 3), the intermediate structure layer is made of metal foil or organic material; preferably, the metal foil is selected from one of copper foil, iron foil, aluminum foil and stainless steel foil; and/or, the organic material is a porous organic film or a non-porous organic film; and/or the organic material is selected from one of polypropylene, polyethylene, polyamide, polyester terephthalate, polyimide, polystyrene and polyvinyl chloride.
In the invention, the adopted intermediate structure layer can be used as a strength layer to ensure the processing performance of the negative pole piece, and the intermediate structure layer can better play the interaction of the upper functional layer and the lower functional layer, thereby further reducing the overpotential of the metal sodium deposition, inhibiting the generation of sodium dendrite and prolonging the cycle life of the battery.
In a second aspect, the negative electrode plate for the sodium-ion battery provided by the invention is obtained by the preparation method of the negative electrode plate for the sodium-ion battery.
Preferably, the negative electrode plate for the sodium-ion battery is formed by a three-layer structure of a first functional layer, an intermediate structure layer and a second functional layer; the first functional layer and the second functional layer are obtained by processing fused spray cloth containing a conductive agent through hydrofluoric acid.
The upper layer and the lower layer are functional layers and are formed by porous melt-blown cloth containing a conductive agent, and the porous melt-blown cloth can absorb a large amount of electrolyte, so that the normal supply of sodium ions in the charging process of the sodium ion battery is ensured, and the overpotential is reduced; meanwhile, the fibers of the melt-blown cloth contain a conductive agent, so that the overpotential in the sodium ion charging process is further reduced, the melt-blown cloth is of a porous structure, sodium ions can be more fully and uniformly deposited on the pores and the surface of the melt-blown cloth in the charging process, and the cycle life of the sodium ion battery is prolonged.
In a third aspect, the present invention provides a sodium ion battery comprising: the negative electrode comprises a negative electrode piece, a positive electrode piece, electrolyte and a diaphragm, wherein the negative electrode piece is the negative electrode piece.
Preferably, the positive electrode sheet includes a positive electrode active material, a conductive agent, a binder, and a current collector.
More preferably, the positive electrode active material is one selected from the group consisting of sodium vanadium phosphate, sodium nickel cobalt manganese oxide, and a prussian blue compound, and is preferably sodium vanadium phosphate.
Further preferably, the conductive agent is one or more selected from acetylene black, carbon nanotubes and graphene, and is preferably carbon black.
More preferably, the binder is one selected from polyvinylidene fluoride, polytetrafluoroethylene and polyacrylic acid, and is preferably polyvinylidene fluoride.
More preferably, the mass ratio of the positive electrode active material to the binder to the conductive agent is 95-98: 1-3: 1-3, preferably 96:2: 2.
Preferably, the current collector is selected from one of aluminum foil and carbon-coated aluminum foil.
Preferably, the separator is selected from any one of polyethylene, polypropylene, polyvinylidene fluoride, and aramid.
Preferably, the electrolyte solution is composed of an organic solvent and an electrolyte sodium salt.
Further preferably, the organic solvent is one or more selected from the group consisting of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluoroethylene carbonate, diethyl ether, diglyme, triglyme, tetraglyme and methyl tert-butyl ether.
Further preferably, the electrolyte sodium salt is selected from one or more of sodium hexafluorophosphate, sodium bifluorosulfonimide, sodium bistrifluoromethanesulfonimide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate and sodium perchlorate.
The invention has the technical effects that: according to the invention, the surface of the negative pole piece is free of the negative active material, when the negative pole piece is charged for the first time, the metal sodium is uniformly deposited on the surface of the negative pole piece and in the internal pores, and the porous conductive fibers are sprayed on the upper layer and the lower layer of the negative pole in a melting mode, so that the overpotential of the metal sodium deposition can be effectively reduced, the generation of sodium dendrite is inhibited, and the cycle performance of the battery is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
In the embodiment of the invention, the adopted melt-blown fabric containing the conductive agent is a self-made melt-blown fabric, a polypropylene raw material and the conductive agent are heated and melted at 180-220 ℃, and the melt-blown fabric is prepared by spinning under the pressure of 5-10 MPa.
Example 1
The embodiment provides a sodium battery negative electrode plate, and a preparation method of the sodium battery negative electrode plate comprises the following specific steps:
1. preparing a melt-blown fabric containing a conductive agent, wherein the thickness of the melt-blown fabric is 2.0 mu m, the porosity is 68%, the mass percentage of the conductive agent in the melt-blown fabric is 56%, and the conductive agent is carbon black;
2. soaking the melt-blown cloth in 10% hydrofluoric acid solution for 8 hours;
3. washing the melt-blown fabric in the step 2 with deionized water to be neutral, and vacuum-drying for 8 hours at 80 ℃;
4. carrying out thermal bonding on a thermal spraying cloth, a 10-micron aluminum foil and the thermal spraying cloth in the upper, middle and lower order to form the negative electrode of the sodium battery, wherein the thermal bonding temperature is 90 ℃, and the thermal bonding pressure is 2 MPa.
This example also provides a 32140 cylindrical sodium ion battery prepared as follows.
1. Preparation of positive pole piece
Adding sodium vanadium phosphate, polyvinylidene fluoride and carbon black (the mass ratio is 96:2: 2) into an organic solvent (preferably N-methyl pyrrolidone), mixing and dispersing uniformly to prepare anode slurry; uniformly coating the positive electrode slurry on the surface of the carbon-coated aluminum foil, drying, and then rolling and slitting to obtain a positive electrode piece;
2. preparation of negative pole piece
Cutting the sodium battery negative electrode product obtained by the method of the embodiment to obtain a negative electrode plate;
3. diaphragm
The diaphragm adopts a Polyethylene (PE) porous polymer film;
4. preparation of the electrolyte
16g of sodium hexafluorophosphate, 25g of ethylene carbonate, 52g of dimethyl carbonate, 6g of diethylene glycol dimethyl ether and 1g of methyl methylthiosulfonate are uniformly mixed to prepare the electrolyte.
5. And winding the positive pole piece, the diaphragm and the negative pole piece into a pole group, rolling a groove, injecting liquid, sealing, and assembling into the 32140 cylindrical sodium-ion battery.
Example 2
1. Preparing a melt-blown fabric containing a conductive agent, wherein the thickness of the melt-blown fabric is 2.5 mu m, the porosity is 82%, the mass percentage of the conductive agent in the melt-blown fabric is 80%, and the conductive agent is acetylene black;
2. soaking the melt-blown cloth in 10% hydrofluoric acid solution for 8 hours;
3. washing the melt-blown fabric in the step 2 with deionized water to be neutral, and vacuum-drying for 8 hours at 80 ℃;
4. carrying out thermal bonding on a melt-blown cloth, an 8-micron polypropylene non-porous film and the melt-blown cloth in the upper, middle and lower order to form the sodium battery cathode, wherein the thermal bonding temperature is 70 ℃, and the thermal bonding pressure is 1.8 MPa.
The cell was prepared as in example 1.
Example 3
1. Preparing a melt-blown fabric containing a conductive agent, wherein the thickness of the melt-blown fabric is 2.3 mu m, the porosity is 71%, the mass percentage of the conductive agent in the melt-blown fabric is 32%, and the conductive agent is carbon black;
2. soaking the melt-blown cloth in 10% hydrofluoric acid solution for 8 hours;
3. washing the melt-blown fabric in the step 2 with deionized water to be neutral, and vacuum-drying for 8 hours at 80 ℃;
4. carrying out thermal bonding on a melt-blown fabric, a 8-micron polyethylene non-porous film and the melt-blown fabric in the upper, middle and lower order to form the sodium battery cathode, wherein the thermal bonding temperature is 70 ℃, and the thermal bonding pressure is 1.6 MPa.
The cell was prepared as in example 1.
Comparative example 1
Only the negative electrode tab in example 1 was replaced with an aluminum foil, and the rest was the same as in example 1.
Comparative example 2
The same as example 1 except that the content of the conductive agent in example 1 was reduced to only 56% to 5%.
Comparative example 3
The HF concentration in example 1 was only reduced to 10% to 1%, otherwise the same as in example 1.
Test examples
The batteries prepared in the examples and comparative examples were charged to 4V at a rate of 0.1C and discharged to 0V at a rate of 0.1C at 25C, and full charge discharge cycle tests were performed until the capacity of the sodium ion battery was less than 80% of the initial capacity, and the first discharge specific capacity and the number of cycles were recorded, and specific data thereof are shown in table 1. Therefore, the sodium-ion battery prepared by the method has higher first discharge capacity and better cycle life.
TABLE 1 test results
| First discharge capacity MAh/g | Number of cycles | |
| Example 1 | 112.7 | 689 |
| Example 2 | 114.6 | 708 |
| Example 3 | 113.3 | 692 |
| Comparative example 1 | 103.2 | 236 |
| Comparative example 2 | 108.2 | 522 |
| Comparative example 3 | 107.6 | 505 |
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a negative pole piece for a sodium ion battery is characterized by comprising the following steps:
1) preparing a melt-blown fabric, and loading a conductive agent on the melt-blown fabric to obtain the melt-blown fabric containing the conductive agent;
2) soaking the melt-blown fabric containing the conductive agent in a hydrofluoric acid solution, washing with water, and drying to obtain a functional layer;
3) thermal bonding is performed in the order of one of the functional layers, one of the intermediate structural layers and the other of the functional layers.
2. The preparation method of the negative electrode plate for the sodium-ion battery according to claim 1, wherein in the step 1), the thickness of the melt-blown fabric is 1-20 μm, and the porosity is 40-80%;
and/or, in the step 1), the conductive agent is selected from one or more of carbon black, acetylene black, carbon fiber and carbon nano tube, and preferably carbon black or acetylene black;
and/or in the step 1), the loading amount of the conductive agent is 10-60%.
3. The method for preparing the negative electrode plate for the sodium-ion battery according to claim 1 or 2, wherein in the step 2), the negative electrode plate is soaked in a 5-10% hydrofluoric acid solution for 5-10 hours.
4. The method for preparing the negative electrode plate for the sodium-ion battery according to claim 3, wherein in the step 2), the water washing is deionized water washing to be neutral; and/or in the step 2), the drying is carried out for 4-10 hours at the temperature of 70-90 ℃ in vacuum.
5. The preparation method of the negative electrode plate for the sodium-ion battery as claimed in any one of claims 1 to 4, wherein in the step 3), the temperature of the thermal bonding is 50-120 ℃; and/or in the step 3), the pressure of the heat bonding is 0.5-10 MPa.
6. The method for preparing the negative electrode plate for the sodium-ion battery as claimed in any one of claims 1 to 5, wherein in the step 3), the intermediate structure layer is made of metal foil or organic material.
7. The method for preparing the negative pole piece for the sodium-ion battery as recited in claim 6, wherein the metal foil is selected from one of copper foil, iron foil, aluminum foil and stainless steel foil; and/or, the organic material is a porous organic film or a non-porous organic film; and/or the organic material is selected from one of polypropylene, polyethylene, polyamide, polyester terephthalate, polyimide, polystyrene and polyvinyl chloride.
8. A negative pole piece for a sodium-ion battery is characterized by being obtained by the preparation method of the negative pole piece for the sodium-ion battery of any one of claims 1 to 7;
preferably, the negative electrode plate for the sodium-ion battery is formed by a three-layer structure of a first functional layer, an intermediate structure layer and a second functional layer; the first functional layer and the second functional layer are obtained by processing fused spray cloth containing a conductive agent through hydrofluoric acid.
9. A sodium ion battery, comprising: the negative pole piece is obtained by the preparation method of the negative pole piece for the sodium-ion battery in any one of claims 1 to 7.
10. The sodium-ion battery of claim 9, wherein the positive electrode sheet comprises a positive active material, a conductive agent, a binder, and a current collector; the positive active material is selected from one of sodium vanadium phosphate, sodium nickel cobalt manganese oxide and Prussian blue compounds; and/or the conductive agent is selected from one or more of acetylene black, carbon nano tubes and graphene; and/or the binder is selected from one of polyvinylidene fluoride, polytetrafluoroethylene and polyacrylic acid;
and/or the current collector is selected from one of aluminum foil and carbon-coated aluminum foil;
and/or the diaphragm is selected from any one of polyethylene, polypropylene, polyvinylidene fluoride and aramid fiber;
and/or the electrolyte consists of an organic solvent and an electrolyte sodium salt; preferably, the organic solvent is one or more selected from ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl acetate, ethyl propionate, fluoroethylene carbonate, diethyl ether, diglyme, triglyme, tetraglyme and methyl tert-butyl ether; and/or the electrolyte sodium salt is selected from one or more of sodium hexafluorophosphate, sodium bifluorosulfonimide, sodium bistrifluoromethanesulfonimide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate and sodium perchlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210116601.3A CN114520311A (en) | 2022-02-07 | 2022-02-07 | Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210116601.3A CN114520311A (en) | 2022-02-07 | 2022-02-07 | Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114520311A true CN114520311A (en) | 2022-05-20 |
Family
ID=81596949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210116601.3A Pending CN114520311A (en) | 2022-02-07 | 2022-02-07 | Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114520311A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160062617A (en) * | 2014-11-25 | 2016-06-02 | 울산과학기술원 | Three-dimensional porous-structured current colletor, method of manufacturing the same, electrode including the same, method of manufacturing the same electrode, and electrochemical device including the same current colletor |
| US9564656B1 (en) * | 2015-09-14 | 2017-02-07 | Nanotek Instruments, Inc. | Process for producing alkali metal or alkali-ion batteries having high volumetric and gravimetric energy densities |
| CN106935861A (en) * | 2017-03-23 | 2017-07-07 | 中南大学 | A kind of sodium-ion battery carbon negative pole material and preparation method thereof |
| CN107221640A (en) * | 2017-06-09 | 2017-09-29 | 北京科技大学 | A kind of preparation method of the compound sodium negative pole of sodium-ion battery |
| CN107316975A (en) * | 2017-07-26 | 2017-11-03 | 清华大学深圳研究生院 | A kind of sodium-ion battery negative plate |
| CN110021755A (en) * | 2019-04-17 | 2019-07-16 | 湖南立方新能源科技有限责任公司 | A kind of sodium-ion battery |
| CN113437254A (en) * | 2021-06-26 | 2021-09-24 | 宁德时代新能源科技股份有限公司 | Negative pole piece of sodium ion battery, electrochemical device and electronic equipment |
| CN113716547A (en) * | 2021-09-02 | 2021-11-30 | 北京化工大学 | Method for preparing sodium ion battery negative electrode material by using waste medical mask |
-
2022
- 2022-02-07 CN CN202210116601.3A patent/CN114520311A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160062617A (en) * | 2014-11-25 | 2016-06-02 | 울산과학기술원 | Three-dimensional porous-structured current colletor, method of manufacturing the same, electrode including the same, method of manufacturing the same electrode, and electrochemical device including the same current colletor |
| US9564656B1 (en) * | 2015-09-14 | 2017-02-07 | Nanotek Instruments, Inc. | Process for producing alkali metal or alkali-ion batteries having high volumetric and gravimetric energy densities |
| CN106935861A (en) * | 2017-03-23 | 2017-07-07 | 中南大学 | A kind of sodium-ion battery carbon negative pole material and preparation method thereof |
| CN107221640A (en) * | 2017-06-09 | 2017-09-29 | 北京科技大学 | A kind of preparation method of the compound sodium negative pole of sodium-ion battery |
| CN107316975A (en) * | 2017-07-26 | 2017-11-03 | 清华大学深圳研究生院 | A kind of sodium-ion battery negative plate |
| CN110021755A (en) * | 2019-04-17 | 2019-07-16 | 湖南立方新能源科技有限责任公司 | A kind of sodium-ion battery |
| CN113437254A (en) * | 2021-06-26 | 2021-09-24 | 宁德时代新能源科技股份有限公司 | Negative pole piece of sodium ion battery, electrochemical device and electronic equipment |
| CN113716547A (en) * | 2021-09-02 | 2021-11-30 | 北京化工大学 | Method for preparing sodium ion battery negative electrode material by using waste medical mask |
Non-Patent Citations (1)
| Title |
|---|
| YU YUAN ET AL.: "Heteroatom-doped carbon-based materials for lithium and sodium ion batteries" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105304936B (en) | A kind of lithium rechargeable battery | |
| JP2023548105A (en) | Sodium ion battery negative electrode pieces, electrochemical devices and electronic devices | |
| US20140043727A1 (en) | Polyimide Capacitance Battery and Manufacturing Method Thereof | |
| CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
| WO2023186165A1 (en) | Sodium-ion battery, and preparation method therefor and use thereof | |
| CN111969164A (en) | Composite modified diaphragm for lithium-sulfur battery and preparation method thereof | |
| WO2021179740A1 (en) | Diaphragm-negative electrode material of integrated structure and preparation method therefor, and secondary battery | |
| CN111653834B (en) | Aqueous electrolyte, aqueous metal ion battery, and method for producing same | |
| CN113046768B (en) | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery | |
| CN110416492A (en) | Negative pole piece and electrochemical battery | |
| CN113644251B (en) | Hollow-structure silicon-carbon anode material and preparation method thereof | |
| CN110690433B (en) | Silicon-based negative electrode material for lithium ion battery and preparation method thereof | |
| CN109859951A (en) | A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof | |
| CN112421185A (en) | Electrolyte of non-negative secondary lithium battery, non-negative secondary lithium battery and formation process | |
| CN114695840A (en) | Sodium ion battery positive plate, sodium ion battery and preparation method and system thereof | |
| CN110400923A (en) | Battery negative electrode material, negative electrode material slurry, negative electrode plate and electrochemical battery | |
| CN112259714B (en) | Solid-state battery composite electrode plate, preparation method thereof and solid-state battery comprising solid-state battery composite electrode plate | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN105632774A (en) | Lithium ion capacitor and manufacturing method thereof | |
| CN112952204A (en) | Preparation method of symmetric polymer-based electrode lithium ion full battery | |
| CN114520311A (en) | Negative pole piece for sodium ion battery, preparation method of negative pole piece and sodium ion battery | |
| CN109817467A (en) | A kind of composite positive pole and preparation method thereof and a kind of electrochmical power source and preparation method thereof | |
| CN112670478B (en) | Carbon sphere packaged amorphous vanadium-oxygen cluster composite material, preparation method thereof and sodium storage application | |
| CN108666551A (en) | A kind of graphene/LiTi2(PO4)3Lithium cell cathode material and preparation method | |
| CN110323079B (en) | High-voltage-resistant anion exchange electrolyte membrane and solid-state battery capacitor thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231120 Address after: 211399 Factory Building No. 6, Phase II, Standard Factory Building, No. 86 Shuanggao Road, Economic Development Zone, Gaochun District, Nanjing City, Jiangsu Province Applicant after: Nanjing Bifeida New Energy Technology Co.,Ltd. Address before: 116450 No. 11, East Rose Street, Huayuankou Economic Zone, Dalian City, Liaoning Province Applicant before: DALIAN CBAK POWER BATTERY CO.,LTD. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220520 |
|
| RJ01 | Rejection of invention patent application after publication |