CN114597077B - Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor - Google Patents
Application of pre-lithiated carbon negative electrode material in sodium ion capacitor and potassium ion capacitor Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 118
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 30
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 30
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 38
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 58
- 238000009830 intercalation Methods 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 26
- 230000002687 intercalation Effects 0.000 claims description 24
- 239000006258 conductive agent Substances 0.000 claims description 23
- 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 18
- 239000011734 sodium Substances 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 11
- 239000011247 coating layer 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
- 238000004146 energy storage Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910021385 hard carbon Inorganic materials 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000006183 anode active material Substances 0.000 claims description 5
- 238000006138 lithiation reaction Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010248 power generation Methods 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 5
- 229940037179 potassium ion Drugs 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- CDFDJGUTYJLKSQ-UHFFFAOYSA-M lithium;naphthalene-1-carboxylate Chemical compound [Li+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 CDFDJGUTYJLKSQ-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- NOYXOVXGCXZLKL-UHFFFAOYSA-N [Na].[Na].C(=O)=C1C(C(=C1O)O)=C=O Chemical compound [Na].[Na].C(=O)=C1C(C(=C1O)O)=C=O NOYXOVXGCXZLKL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The application belongs to the technical field of super capacitors, and particularly relates to application of a pre-lithiated carbon negative electrode material in a sodium ion capacitor and a potassium ion capacitor. The metal ion capacitor consists of a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate comprises a negative current collector and a negative active material, and the negative active material comprises an internal carbon material and a lithium-containing SEI layer positioned on the surface of the carbon material; the positive electrode material is activated carbon. The metal ion capacitor prepared by the application has the same power density and energy density as the traditional metal ion capacitor, and has the advantages of simple preparation process, better safety performance and contribution to industrial production.
Description
Technical Field
The application belongs to the technical field of super capacitors, and particularly relates to a metal ion capacitor and a preparation method thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the application and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Under the increasingly worsened environmental problems and the increasing demand for sustainable new energy, new hybrid capacitors with both high energy density and high power density are becoming one of the key developments. Since amatuci et al proposed the concept of a hybrid capacitor in 2001, lithium ion capacitors have been widely studied and used as a promising energy storage device. However, the lithium element has a small content in the crust, and the cost is high, so that the lithium element cannot be applied on a large scale. Therefore, sodium ion capacitors and potassium ion capacitors, which have similar physicochemical properties to lithium elements and are abundant in reserves and low in cost, are attracting attention of researchers.
The metal ion capacitor is used as a novel energy storage device and mainly comprises a battery type negative electrode and a capacitor type positive electrode, and has the advantages of high power density, long cycle life, high charge and discharge rate, high safety and the like. Generally, such capacitors mainly use porous carbon materials with large specific surface area, such as activated carbon, as a positive electrode material, and use materials for energy storage through reversible ion intercalation and deintercalation as a negative electrode material. The combination of different energy storage mechanisms during charge-discharge results in a metal ion capacitor having a higher energy density than a conventional electric double layer capacitor, while having a higher power density than a metal ion battery.
For the double-carbon-based metal ion capacitor, the anode material and the cathode material are both carbon-based materials, and due to the special structure of the carbon-based materials, in the initial cycle, electrolyte is subjected to irreversible electrochemical reaction on the electrode surface and forms an SEI layer, so that a large amount of active sodium/potassium is consumed, the available energy density is greatly limited, and the performance of the metal ion capacitor is obviously lower than the optimal value. There is currently a very limited ability to improve the performance of metal ion capacitors by changing the structure of the electrode material, as well as by adjusting the electrolyte. The successful application of the pre-lithiation technology in the lithium ion capacitor provides another idea for improving the performance of the energy storage device: through a pre-metallization technology, the surface of the anode material is adjusted, a stable SEI layer is formed in advance to reduce irreversible loss of metal ions in the electrolyte, and meanwhile, the defect of a carbon-based material metal source is supplemented. Therefore, in the development of metal ion capacitors, the application of the pre-embedded metal technology is important in order to optimize the performance of the metal ion capacitors.
Chinese patent CN110335764a discloses a pre-sodiumizing method for efficiently constructing sodium ion capacitor by using one of sodium rose bengal, disodium crotonate, 1, 2-dicarbonyl-3, 4-dihydroxy-3-cyclobutene disodium salt as sodium source additive. However, the reduction product formed after the sodium source additive is removed from sodium in the technical scheme is dissolved into the electrolyte solvent, and has adverse effects on the energy density and the cycle performance of the sodium ion capacitor. Chinese patent publication No. CN113113235a discloses a sodium ion capacitor and a negative electrode pre-sodiumizing method thereof, sodium oxalate and/or sodium carbonate are used as a sodium source additive for the negative electrode pre-sodiumizing of the sodium ion capacitor. However, in the technical scheme, the safety performance of the capacitor is influenced by the gas formed after the sodium source additive is removed. Chinese patent CN109686924a discloses a technique of pre-embedding potassium ions on a metal anode foil, which improves coulombic efficiency by forming an SEI film layer and/or a potassium-metal alloy layer on the surface of the metal foil. However, the potassium ion radius is too large, so that the structure is easily damaged and pulverized in the repeated deintercalation process of the cathode. In addition to the currently proposed relatively advanced pre-sodium or pre-potassium techniques, the traditional method for pre-metallizing by using metal sodium powder or metal potassium powder is poor in safety performance in the industrial production process due to high activity of metal sodium and metal potassium, which are prone to explosion. Therefore, the existing mature pre-lithiation technology is easier for industrial production and has high safety performance.
Disclosure of Invention
In order to solve the problems of low coulombic efficiency, poor cycle performance and the like caused by continuous consumption of metal ions in electrolyte due to continuous formation of an SEI layer on the surface of an electrode in the cycle process of the traditional metal ion capacitor, the application aims to provide a preparation method of a sodium ion capacitor and a potassium ion capacitor.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect of the present application, there is provided a metal ion capacitor having a negative electrode pre-intercalated with lithium, comprising: positive plate, negative plate, diaphragm and electrolyte;
the negative electrode sheet comprises a negative electrode current collector and a negative electrode coating layer coated on the surface of the negative electrode current collector, wherein the negative electrode coating layer comprises a negative electrode active material, a conductive agent and a binder;
wherein the negative electrode active material is a pre-lithiated carbon material.
According to the application, the pre-lithiated carbon cathode material is adopted, and firstly, lithium ions are pre-inserted into the carbon material, so that a lithium source is provided for the carbon cathode material of the sodium ion capacitor and the potassium ion capacitor, and the lithium source plays the same role as a sodium source or a potassium source in the capacitor. Compared with the sodium source provided by the prior pre-sodium treatment and the potassium source provided by the pre-potassium treatment, the sodium and potassium metal have high activity, the safety performance is low in the pre-metallization process, the operability is poor, the maturity of the pre-lithiation technology is high, and the safety is better in industrial production; secondly, a compact lithium-containing SEI layer is formed on the surface of the carbon cathode material in advance, so that consumption of metal ions in electrolyte caused by formation of the SEI layer in the first charge and discharge process of the capacitor is reduced, and electrochemical performance of the capacitor is improved.
In a second aspect of the present application, there is provided a method for manufacturing a metal ion capacitor having a cathode pre-intercalated with lithium, comprising:
mixing a negative electrode active material, a conductive agent and a binder, and coating the mixture on a negative electrode current collector to obtain a negative electrode precursor;
pre-lithiating the negative electrode precursor to form a negative electrode plate;
mixing an anode active material, a conductive agent and a binder, and then rolling into a sheet to be coated on an anode current collector to obtain an anode sheet;
and assembling the pre-lithiated negative electrode plate with the positive electrode plate, the diaphragm and the electrolyte to obtain the metal ion capacitor.
In a third aspect of the application, there is provided the use of a metal ion capacitor as described above in the field of energy storage.
The application has the beneficial effects that:
(1) The carbon material has low price and stable performance, is easy to disperse and prepare the cathode slurry in the use process, and has lower overall preparation cost;
(2) Due to the special structure of the carbon materials of the anode and the cathode, the metal ion capacitor continuously forms an SEI layer on the surface of the electrode in the circulation process, and the electrolyte is continuously consumed. The electrode is subjected to pre-lithiation treatment, so that metal ion consumption of the cathode in the first charge and discharge process can be compensated, a compact SEI layer is formed preferentially, the structural integrity of the electrode is ensured, and the cycling stability of the capacitor is improved; and meanwhile, the voltage working window can be widened, and the energy density of the capacitor can be improved.
(3) Compared with pre-potassium or sodium, the pre-lithium process has higher maturity and better safety performance, and is easier for industrial production. Meanwhile, the compact SEI layer formed in the pre-lithium intercalation process improves the interface dynamics of the metal ion capacitor electrode, and is beneficial to improving the rate capability.
(4) The method has the advantages of simplicity, low cost, universality and easiness in large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is a graph showing time-voltage curves of sodium ion capacitors prepared in example 1 of the present application;
FIG. 2 is the rate capability of the sodium capacitor prepared in example 1 of the present application;
FIG. 3 is a graph showing the cycle performance of the sodium ion capacitor prepared in example 1 of the present application;
FIG. 4 is a graph showing time-voltage curves of a potassium ion capacitor prepared in example 10 of the present application;
FIG. 5 is the rate capability of the potassium-ion capacitor prepared in example 10 of the present application;
FIG. 6 shows the cycle performance of the potassium ion capacitor prepared in example 10 of the present application.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The application provides a metal ion capacitor (sodium ion capacitor and potassium ion capacitor) and a preparation method thereof.
The application provides a metal ion capacitor, which comprises a positive plate, a negative plate, a diaphragm and electrolyte; the negative electrode sheet comprises a negative electrode current collector and a negative electrode coating layer coated on the surface of the negative electrode current collector, wherein the negative electrode coating layer comprises a negative electrode active material, a conductive agent and a binder;
the positive plate comprises a positive current collector and a positive coating layer coated on the surface of the positive current collector, wherein the positive coating layer comprises a positive active material, a conductive agent and a binder;
the negative electrode active material is a pre-lithiated carbon material and comprises an internal carbon material and a lithium-containing SEI layer on the surface of the carbon material;
the positive electrode active material is a porous carbon material.
In the application, the negative electrode active material is a carbon material, and the carbon material has low price and stable performance, is easy to disperse in the use process, is easy to prepare the negative electrode slurry, and has lower overall preparation cost. Further, the unique structure of the carbon material provides various energy storage mechanisms for ion storage, and further improves the energy density of the metal ion capacitor. Meanwhile, the potential of the carbon material is lower, the voltage working window can be widened, and the energy density of the capacitor is further improved.
The carbon material is one or more of graphite, mesophase carbon microspheres, hard carbon and soft carbon.
In the application, the active carbon is preferable in the positive electrode active material, and the active carbon has large specific surface area, adjustable pore diameter structure, good conductivity and high chemical stability, thus being the most widely used supercapacitor electrode material at present.
In the application, the negative electrode current collector is a copper foil. The negative electrode current collector is preferably copper foil because the potential of the negative electrode is low and the aluminum foil or other current collector undergoes an alloying reaction with lithium at low potential.
In the application, the positive current collector of the positive plate is a stainless steel mesh, a foam nickel plate or an aluminum foil. The positive electrode potential is high, many metals (such as copper) are easily oxidized under high potential, and the aluminum foil is stable under high potential due to the existence of an oxide layer, so the positive electrode current collector is preferably aluminum foil.
In the application, the positive plate and the negative plate also comprise a conductive agent and a binder. Wherein the conductive agent is one or more of graphite powder, carbon black and acetylene black for increasing the conductivity of the active material. The binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene and water-soluble rubber which are used for binding the active material on the surface of the current collector.
In some embodiments, the above-mentioned binder and conductive agent are beneficial to improving the strength and electrical properties of the positive and negative plates, and those skilled in the art can select reasonable binder and conductive agent with reference to the prior art, and will not be described herein.
In the present application, the electrolyte contains sodium salt for the sodium ion capacitor. The sodium salt is NaPF 6 、NaClO 4 One or more of naffsi;
for potassium ion capacitors, the electrolyte contains potassium salts. The potassium salt is KPF 6 、KClO 4 One or more of KTFSI.
The solvent in the electrolyte is one or more of EC, DEC, DMC, EMC, FEC, DOL, DMSO, PC.
In the application, the method for pre-embedding lithium is a half-cell pre-embedding lithium method, a short-circuit pre-embedding lithium method, a direct contact pre-embedding lithium method or a chemical pre-embedding lithium method.
The capacities of the positive and negative electrodes are generally different, but under the condition of conservation of charge (that is, electrons obtained by one electrode are at most given by the other electrode), the capacity of the whole capacitor is determined by the battery with the lowest capacity. Therefore, the mass ratio of the anode to the cathode needs to be controlled in a certain proportion, and the capacity of the capacitor cannot be increased by blindly increasing the mass of one of the anode and the cathode, but the capacity is reduced due to the fact that the migration distance of ions or electrons is increased due to the fact that the electrode is too thick. Thus, the mass of the active material increases, the capacity decreases, and the specific capacity decreases. Thus, in the present application, the mass ratio of the anode active material to the cathode active material is 3:1 to 1:3.
The preparation method of the metal ion capacitor provided by the application comprises the following steps:
mixing a negative electrode active material, a conductive agent and a binder, and coating the mixture on a negative electrode current collector to obtain a negative electrode precursor; pre-lithiating the negative electrode precursor to form a negative electrode plate;
mixing an anode active material, a conductive agent and a binder, and then rolling into a sheet to be coated on an anode current collector to obtain an anode sheet;
and assembling the pre-lithiated negative electrode plate with the positive electrode plate, the diaphragm and the electrolyte to obtain the metal ion capacitor.
In the application, the preparation process of the negative plate is as follows: the method for pre-embedding lithium is a half-cell pre-embedding lithium method, a direct contact pre-embedding lithium method or a chemical pre-embedding lithium method.
The half-cell pre-lithium intercalation method comprises the following steps: the negative electrode piece is used as a working electrode, the lithium piece is used as a counter electrode, the middle is provided with a diaphragm and electrolyte to assemble a half battery, the battery is circulated for 1-10 circles at 0.01-3V with 0.01-1A/g, and then the voltage is reduced to 0.01V.
The short circuit pre-lithium intercalation method comprises the following steps: and taking the negative electrode plate as a working electrode, taking the lithium plate as a counter electrode, putting the lithium plate into lithium battery electrolyte, and shorting the working electrode and the counter electrode with a direct external lead for 0.5-15 h.
The direct contact pre-lithium intercalation method comprises the following steps: and (3) taking the negative electrode plate as a working electrode, taking the lithium plate as a counter electrode, dripping lithium salt-containing electrolyte on the surface of metal lithium, and then directly contacting the negative electrode plate with the metal for 0.5-12 h to obtain the pre-lithiated negative electrode plate.
The chemical pre-lithium intercalation method comprises the following steps: at room temperature, soaking the negative electrode plate in a lithium-containing aromatic hydrocarbon composite solution of 0.5-2 mol/L for 5-10min to obtain the pre-lithiated negative electrode plate. Wherein the aromatic hydrocarbon compound solution comprises one or a mixture of more of biphenyl, biphenyl derivatives, anthracene derivatives, naphthalene and naphthalene derivatives.
Aromatic compounds are more likely to form complexes with lithium metal and have no effect on the reaction, and thus aromatic compounds are selected.
In the application, the mass ratio of the cathode slice carbon material to the conductive agent to the binder is 60-95:2-40:1-10. The choice of conductive agent and binder is consistent with that described above.
In the application, the mass ratio of the anode sheet porous carbon material to the conductive agent to the binder is 60-95:2-40:1-10. The choice of conductive agent and binder is consistent with that described above.
In the present application, the process of assembling the metal ion capacitor is: in a glove box protected by argon, the positive plate, the diaphragm and the negative plate are sequentially overlapped to form a compact structure, and electrolyte is injected.
The application also provides a preparation method of the metal ion capacitor, which comprises the following steps:
step one: preparing a negative electrode plate, namely uniformly mixing a carbon material, a conductive agent and a binder in proportion, coating the mixture on a copper foil, rolling the mixture into a sheet, drying the sheet, cutting the sheet into a rectangle or a circle, and performing pre-lithium embedding treatment to obtain the negative electrode plate;
step two: preparing a positive plate, namely uniformly mixing active carbon, a conductive agent and a binder according to a proportion, coating the mixture on a stainless steel mesh, a foam nickel plate or an aluminum foil, rolling the mixture into a sheet, drying the sheet, and finally cutting the sheet into a rectangle or a circle to obtain the positive plate;
step three: and assembling the metal ion capacitor, sequentially superposing the positive plate, the diaphragm and the negative plate to form a compact structure, and injecting electrolyte.
The application will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Examples 1 to 9 are sodium ion capacitor examples
Example 1
Step one: preparing a negative electrode plate, namely uniformly mixing hard carbon, carbon black and a binder (PVDF) according to a mass ratio of 8:1:1, adding an appropriate amount of NMP to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, and cutting the electrode plate Cheng Yuanpian after vacuum drying at 80 ℃ for 12 hours;
the cut pole piece is pre-embedded with lithium, the method for pre-embedding lithium is half-cell pre-embedding lithium, and the steps are as follows: the negative electrode piece is used as a working electrode, the lithium piece is used as a counter electrode, the battery is assembled, and after the battery is cycled between 0.01 and 3V for 3 circles at a low current density of 0.1A/g, the voltage is reduced to 0.01V. Taking out the negative electrode plate after disassembling the battery, and drying to obtain the negative electrode plate after pre-embedding lithium.
Step two: preparing a positive plate, namely uniformly mixing active carbon, carbon black and a binder (PTFE) according to a mass ratio of 8:1:1 to obtain positive electrode slurry, rolling the positive electrode slurry into a sheet, drying at 120 ℃ for 12 hours, and then placing the sheet on an aluminum foil to obtain the positive plate of the sodium ion capacitor;
step three: assembling the sodium ion capacitor, sequentially superposing a positive plate, a diaphragm and a negative plate in a glove box protected by argon to form a compact structure, wherein the active mass ratio of the positive electrode to the negative electrode is 1:1, and then injecting 1M NaPF 6 in EC DMC emc=1:1:1 vol% electrolyte.
As shown in fig. 1, the voltage-time curve of the sodium ion capacitor prepared by the above method exhibits an ideal triangle;
as shown in FIG. 2, the capacitor can have capacities of 22mAh/g, 14mAh/g, 8mAh/g and 4mAh/g respectively at current densities of 0.1A/g, 0.5A/g, 1A/g and 5A/g, and shows good multiplying power performance;
as shown in FIG. 3, the cycle had a capacity of 21mAh/g at a current density of 0.5A/g, and after 2000 cycles the capacity was 18.6mAh/g, and the capacity retention was 88.6%, showing good cycle performance.
Example 2
The sodium ion capacitor provided in this embodiment is basically identical to that in embodiment 1, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a direct contact pre-lithium intercalation method, and includes the following steps: and taking the negative electrode plate as a working electrode, taking the lithium plate as a counter electrode, dripping lithium salt-containing electrolyte on the surface of metal lithium, and then directly contacting the negative electrode plate with the metal for 5 hours to obtain the pre-embedded lithium negative electrode plate.
Example 3
The sodium ion capacitor provided in this embodiment is basically identical to that in embodiment 1, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a chemical pre-lithium intercalation method, and includes the following steps: at room temperature, soaking the negative electrode plate in 1ml of 0.5mol/L lithium naphthalate for 5min to obtain the pre-lithiated negative electrode plate.
Example 4
The sodium ion capacitor provided in this embodiment is basically identical to that in embodiment 1, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a short-circuit pre-lithium intercalation method, and includes the following steps: and connecting a working electrode of an electrochemical workstation with a negative electrode, connecting a counter electrode and a reference electrode with a lithium sheet, then connecting the lithium sheet with the negative electrode by using a metal sheet to enable the lithium sheet and the negative electrode to perform natural short-circuit discharge, and simultaneously monitoring the potential of the negative electrode to stop short-circuit when the potential of the negative electrode is reduced to 0.01V, thus obtaining the pre-lithiated negative electrode sheet.
Example 5
The sodium ion capacitor provided in this example was substantially identical to that in example 1, except that the negative electrode carbon material was soft carbon during the preparation of the negative electrode sheet.
Example 6
The sodium ion capacitor provided in this example was substantially identical to that in example 1, except that the negative electrode carbon material was glucose-sintered carbon spheres during the preparation of the negative electrode sheet.
Example 7
The sodium ion capacitor provided in this example was substantially identical to that of example 1, except that the mass ratio of the positive electrode material (porous carbon material) to the negative electrode material (hard carbon) was 1:2 during capacitor assembly.
Example 8
The sodium ion capacitor provided in this example is substantially identical to that of example 1, except that during capacitor assembly, the electrolyte is 1M NaCIO 4 Dissolved in EC DMC emc=1:1:1% fec.
Example 9
The present example provides a sodium ion capacitor substantially identical to that of example 1, except that during capacitor assembly, the electrolyte is 1M NaPF 6 Dissolved in EC DMC emc= 1:1:1Vol%with 5%FEC.
Table one is a summary of the energy density, power density, and capacity retention after 2000 cycles for sodium ion capacitors prepared in examples 1-9.
List one
Examples 10 to 20 are potassium ion capacitor examples
Example 10
(1) Preparation of negative electrode sheet
Mixing hard carbon, carbon black (super P) and PVDF in a mass ratio of 8:1:1, adding a proper amount of solvent NMP, uniformly mixing, and coating on a copper foil; drying at 80deg.C under vacuum for 12 hr; cutting the dried pole piece into a round shape.
The cut pole piece is pre-embedded with lithium, the method for pre-embedding lithium is half-cell pre-embedding lithium, and the steps are as follows: the negative electrode piece is used as a working electrode, the lithium piece is used as a counter electrode, the battery is assembled, and after the battery is cycled between 0.01 and 3V for 3 circles at a low current density of 0.1A/g, the voltage is reduced to 0.01V. Taking out the negative electrode plate after disassembling the battery, and drying to obtain the negative electrode plate after pre-embedding lithium.
(2) Preparation of positive plate
Uniformly mixing active carbon, carbon black and a binder (PTFE) according to a mass ratio of 8:1:1 to obtain positive electrode slurry, rolling the positive electrode slurry into a sheet, drying at 120 ℃ for 12 hours, and placing the sheet on an aluminum foil to obtain a positive electrode sheet of the potassium ion capacitor;
(3) Assembly of potassium ion capacitor
In a glove box protected by argon, sequentially superposing a positive electrode plate, a diaphragm and a negative electrode plate to form a compact structure, wherein the active mass ratio of the positive electrode to the negative electrode is 1:1, and then injecting 1M KPF6 in EC:DMC:EMC =4:3:2Vol% electrolyte.
As shown in fig. 4, the voltage-time curve of the sodium/potassium ion capacitor prepared by the above method exhibits an ideal triangle;
as shown in FIG. 5, the capacitor can have the capacities of 44mAh/g, 30mAh/g, 15mAh/g and 4mAh/g respectively at the current densities of 0.1A/g, 0.5A/g, 1A/g and 5A/g, and has good multiplying power performance;
as shown in FIG. 6, the cycle had a capacity of 47mAh/g at a current density of 0.5A/g, and after 2000 cycles the capacity was 46mAh/g, and the capacity retention was 97.87%, showing good cycle performance.
Example 11
The potassium ion capacitor provided in this example was basically the same as that in example 10, except that the negative electrode carbon material was soft carbon during the preparation of the negative electrode sheet.
Example 12
The potassium ion capacitor provided in this example was substantially identical to that in example 10, except that the negative electrode carbon material was graphite during the preparation of the negative electrode sheet.
Example 13
The potassium ion capacitor provided in this example was substantially identical to that in example 10, except that the negative electrode carbon material was a mesophase carbon microsphere in the preparation process of the negative electrode sheet.
Example 14
The present example provides a potassium ion capacitor substantially identical to that of example 10, except that during capacitor assembly, the electrolyte was 1M KPF 6 Dissolved in EC DMC EMC =4:3:2Vol％with 5％FEC。
Example 15
The present example provides a potassium ion capacitor substantially identical to that of example 10, except that during capacitor assembly, the electrolyte was 1M KCIO 4 Dissolved in EC DMC emc=4: 3:2Vol% with 5% FEC.
Example 16
The potassium ion capacitor provided in this embodiment is basically identical to that in embodiment 10, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a direct contact pre-lithium intercalation method, comprising the steps of: and taking the negative electrode plate as a working electrode, taking the lithium plate as a counter electrode, dripping lithium salt-containing electrolyte on the surface of metal lithium, and then directly contacting the negative electrode plate with the metal for 5 hours to obtain the pre-embedded lithium negative electrode plate.
Example 17
The potassium ion capacitor provided in this embodiment is basically identical to that in embodiment 10, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a chemical pre-lithium intercalation method, comprising the steps of: at room temperature, soaking the negative electrode plate in 1ml of 0.5mol/L lithium naphthalate composite solution for 5min to obtain the pre-lithiated negative electrode plate.
Example 18
The potassium ion capacitor provided in this embodiment is basically identical to that in embodiment 10, except that in the preparation of the negative electrode sheet, the pre-lithium intercalation method adopts a short-circuit pre-lithium intercalation method, and includes the following steps: and connecting a working electrode of an electrochemical workstation with a negative electrode, connecting a counter electrode and a reference electrode with a lithium sheet, then connecting the lithium sheet with the negative electrode by using a metal sheet to enable the lithium sheet and the negative electrode to perform natural short-circuit discharge, and simultaneously monitoring the potential of the negative electrode to stop short-circuit when the potential of the negative electrode is reduced to 0.01V, thus obtaining the pre-lithiated negative electrode sheet.
Example 19
The potassium ion capacitor provided in this example was substantially identical to that in example 10, except that the mass ratio of the positive electrode material (porous carbon material) to the negative electrode material (hard carbon) was 1:2 during capacitor assembly.
Example 20
The potassium ion capacitor provided in this example was substantially identical to that in example 10, except that the mass ratio of the positive electrode material (porous carbon material) to the negative electrode material (hard carbon) was 2:1 during capacitor assembly.
Table II summarizes the energy density and power density of the potassium ion capacitors prepared in examples 10-20.
Watch II
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present application, and the present application is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. An application of a metal ion capacitor with a pre-embedded lithium cathode in the field of energy storage is characterized in that,
the metal ion capacitor with the cathode pre-embedded with lithium comprises: positive plate, negative plate, diaphragm and electrolyte;
the negative electrode sheet comprises a negative electrode current collector and a negative electrode coating layer coated on the surface of the negative electrode current collector, wherein the negative electrode coating layer comprises a negative electrode active material, a conductive agent and a binder;
wherein the negative electrode active material is a pre-lithiated carbon material;
the metal ion capacitor is a sodium ion capacitor or a potassium ion capacitor, and the electrolyte of the sodium ion capacitor contains sodium salt, wherein the sodium saltIs NaPF 6 、NaClO 4 One or more of naffsi;
the electrolyte of the potassium ion capacitor contains potassium salt which is KPF 6 、KClO 4 One or more of KTFSI;
the solvent in the electrolyte is one or more of EC, DEC, DMC, EMC, FEC, DOL, DMSO, PC;
the pre-lithiated carbon material includes: the solid electrolyte comprises a carbon material containing lithium inside and a lithium-containing SEI film positioned on the surface of the carbon material.
2. The use of claim 1, wherein the carbon material is one or more of graphite, mesophase carbon microspheres, hard carbon, soft carbon;
the negative electrode current collector is a copper foil or an aluminum foil.
3. The use according to claim 1, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode coating layer coated on the surface of the positive electrode current collector, the positive electrode coating layer comprising a positive electrode active material, a conductive agent, and a binder;
the positive electrode active material is a porous carbon material;
the porous carbon material is an active carbon material;
the positive current collector of the positive plate is a stainless steel mesh, a foam nickel plate or an aluminum foil.
4. The use according to claim 1, wherein the conductive agent is one or more of graphite powder, carbon black, acetylene black;
the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene and water-soluble rubber;
the mass ratio of the anode active material to the cathode active material is 3:1-1:3.
5. The use according to claim 1, wherein the energy storage device is used in consumer electronics, electric automobiles, wind power generation, rail transit or heavy machinery.
6. A method of manufacturing a metal ion capacitor after lithium pre-intercalation of a negative electrode for use according to any one of claims 1 to 5, comprising:
mixing a negative electrode active material, a conductive agent and a binder, and coating the mixture on a negative electrode current collector to obtain a negative electrode precursor;
pre-lithiating the negative electrode precursor to form a negative electrode plate;
mixing an anode active material, a conductive agent and a binder, and then rolling into a sheet to be coated on an anode current collector to obtain an anode sheet;
and assembling the pre-lithiated negative electrode plate with the positive electrode plate, the diaphragm and the electrolyte to obtain the metal ion capacitor.
7. The method for manufacturing a metal ion capacitor after lithium intercalation in advance of a negative electrode according to claim 6, wherein the mass ratio of the negative electrode active material or the positive electrode active material to the conductive agent and the binder is 60-95:2-40:1-10;
the pre-lithiation method is a half-cell pre-lithium-intercalation method, a short-circuit pre-lithium-intercalation method, a direct contact pre-lithium-intercalation method or a chemical pre-lithium-intercalation method;
the half-cell pre-lithium intercalation method has the voltage range of 0.01-3V, the current range of 0.01-1A/g, the cycle number of 1-10, and the cut-off voltage of 0.01V;
short-circuit time of the short-circuit pre-lithium intercalation method is 0.5-15 h;
the contact time of the direct contact pre-lithium intercalation method is 0.5 to 12 hours;
the chemical pre-lithium intercalation method is to soak in the lithium-containing aromatic hydrocarbon composite solution for 5 to 10 minutes;
the process of assembling the metal ion capacitor is as follows: in a glove box protected by argon, the positive plate, the diaphragm and the negative plate are sequentially overlapped to form a compact structure, and electrolyte is injected.
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