CN111105937A - Super capacitor or metal pre-embedded cathode and preparation method thereof - Google Patents
Super capacitor or metal pre-embedded cathode and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 60
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- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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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
- H01G11/84—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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
- 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)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a preparation method of a super capacitor, which utilizes the technology that an electric double layer is used as a negative electrode for metal pre-embedding and is applied to a hybrid super capacitor. The metal pre-embedding method uses the active carbon for adsorbing the metal ion layer as a metal pre-embedding medium, so that compared with the method of directly performing metal pre-embedding by using metal, the metal pre-embedding method has the advantages of obviously improved safety, simple process, controllable metal pre-embedding amount and wide application prospect.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a super capacitor or a metal pre-embedded negative electrode and a preparation method thereof.
Background
The super capacitor is also called as an electrochemical capacitor, is used as an energy storage device, has the characteristics of high power, short charging time, long service life, wide use temperature range, high safety performance and the like, can be used as a high-power pulse power supply, and has very wide development prospect in the fields of wind energy and solar power generation, hybrid electric vehicles, heavy machinery, standby power supplies, portable electronic products and the like. The energy storage mechanism of the super capacitor can be divided into two types: the first type is an electric double layer formed by interfacial charge separation to store energy, and is called an electric double layer capacitor; the second type stores energy by a faradaic pseudocapacitance mechanism associated with the electrode potential generated by a redox reaction on the surface of an electrode or on the bulk of the electrode in two or quasi-two dimensions, and the associated capacitor is called a faradaic pseudocapacitor or a pseudocapacitor. The former mainly depends on the physical electrostatic adsorption of electrolyte ions on the surface of an electrode for energy storage, and the latter mainly depends on the reversible redox reaction generated on the surface of the electrode for energy storage. The surface energy storage mode determines that the energy density of the super capacitor is far lower than that of a battery depending on bulk phase energy storage, and the super capacitor needs to be matched with the battery in practical application, so that the complexity of an energy storage system is increased, and the application range of the super capacitor is limited.
In order to further increase the energy density of the super capacitor, researchers have begun directing attention to a lithium ion capacitor, a novel super capacitor combining a lithium ion battery and a double electric layer super capacitor. Two electrodes of the lithium ion super capacitor are made of different materials, the energy storage mechanisms of the two electrodes are different, one electrode is made of an active carbon material for storing energy by a double electric layer, and the other electrode is made of lithium ion battery electrode materials such as graphite, hard carbon, titanium dioxide, lithium titanate, lithium manganate and the like. Among them, the activated carbon-hard carbon type lithium ion capacitor is widely applied.
In industrial production, lithium is required to be pre-embedded in a negative electrode in the production of a lithium ion super capacitor, so that the manufacturing technology process of the lithium ion capacitor is more complicated than that of an electric double layer capacitor and a lithium ion battery, and finding a proper and reliable pre-embedded lithium technology is a well-known technical difficulty. The same problem exists for other types of metal ion capacitors such as sodium ion capacitors and the like. Taking a lithium ion capacitor as an example, the conventional lithium pre-intercalation method is to assemble a capacitor by using a lithium sheet and a hard carbon electrode to perform a discharge reaction, complete the process of lithium ion intercalation into a hard carbon material, and then take out the hard carbon electrode with pre-intercalation and assemble the hard carbon electrode with an active carbon electrode into the capacitor. Therefore, the lithium embedding amount of the hard carbon electrode can be ensured to be sufficient, the irreversible capacity is eliminated, the potential of the negative electrode is reduced, and the ideal working voltage window selection is realized. However, the lithium-embedded hard carbon electrode has a potential close to that of the lithium sheet, so that the reaction activity is high, the safety is low in the process of taking out and reassembling the capacitor, the capacitor cannot contact air, hidden dangers such as combustion and explosion exist, and the practical application is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a super capacitor or a negative electrode material negative electrode.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a super capacitor or a metal pre-embedded cathode comprises the steps of assembling a metal-activated carbon capacitor by taking a metal material as a cathode and an activated carbon electrode as an anode, and discharging to obtain an activated carbon electrode adsorbing a metal ion layer; then the activated carbon electrode absorbing the metal ion layer is used as an anode and is assembled with a to-be-metal pre-embedded cathode to form an activated carbon-to-be-metal pre-embedded cathode capacitor, charging is carried out to realize metal pre-embedding of the cathode, and finally the super capacitor with the metal pre-embedded electrode as the cathode and the activated carbon electrode as the anode is obtained;
alternatively, the metal pre-embedded negative electrode in the capacitor may be obtained by taking out the negative electrode after metal pre-embedding.
The active carbon electrode or the to-be-metal pre-embedded negative electrode is prepared by the following steps:
(1) dissolving organic polymer resin in an organic solvent or water, and stirring for 0.5-2 hours at the temperature of 20-100 ℃ to form a corresponding polymer solution;
(2) adding a conductive agent and an active carbon material or a negative electrode material into the solution, and fully stirring for 2-10 hours at the temperature of 20-50 ℃ to finally prepare a blending solution; wherein the solid content is 5-40 wt%;
(3) scraping the blended solution obtained in the step (2) on an aluminum foil to form a whole, and drying for 2-48 h to obtain a finished product of an activated carbon electrode or a to-be-metal pre-embedded negative electrode;
the organic solvent is one or more than two of DMSO, DMAC, NMP and DMF.
The active material loading of the active carbon electrode or the to-be-metal pre-embedded negative electrode is 1mg cm-3～10mg cm-3。
The mass of the organic polymer resin in the active carbon electrode or the to-be-metal pre-embedded negative electrode accounts for 3-60 wt% of the total mass of the electrode; the conductive agent accounts for 5-20 wt% of the total mass of the electrode;
the active carbon or the negative electrode material accounts for 30-90 wt% of the whole electrode.
The organic polymer resin is one or more of Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), Polystyrene (PS), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), polyether sulfone (PES), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); the conductive agent is one or more than two of commercialized carbon nano-tube, graphene, carbon nano-fiber, BP2000, KB600, KB300, XC-72, Super-P, acetylene black and active carbon.
The metal material is one or more than two of metal simple substances or salts capable of releasing metal ions, and the metal is one or more than two of lithium, sodium, magnesium and potassium; the salt capable of releasing metal ions is one or more of LiMO (M ═ one or more of Co, Ni, Fe, Cu and Mn);
the active carbon material is one or more than two mixed materials of active carbon or active carbon and lithium ion battery anode material LiMO (one or more than two of Co, Ni, Fe, Cu and Mn).
The negative electrode material is one or more than two of hard carbon, soft carbon, graphite, silicon-carbon composite material, silicon monoxide and tin-based material. Hard blankets or soft carbons are preferred.
The cut-off voltage of the metal-activated carbon capacitor in the discharging process is 0V to any value less than the initial voltage of the capacitor, and 1.5V is preferred;
in the charging process of the activated carbon-to-be-metal pre-embedded negative electrode capacitor, the initial voltage is used as the initial voltage, and the cut-off voltage is any value from the initial voltage of the capacitor to 4.3V, preferably 4.0V.
The electrolyte adopted by the capacitor adopts EC: DEC 1:1 solvent and LiPF solute6、NaClO4Or KPF6One kind of (1).
The super capacitor or the metal pre-embedded negative electrode prepared by any one of the methods.
The beneficial results of the invention are:
compared with the prior art, the invention utilizes the double electric layers as the technology of the negative metal pre-embedding, only needs to take out the active carbon electrode adsorbing the metal ion layer for assembly, has higher potential and low reaction activity, obviously reduces the irreversible capacity and the working potential of the negative electrode, has good safety, greatly improves the safety of the operation process while realizing the pre-embedding of lithium, and has good application prospect.
Description of the drawings:
FIG. 1: the charge-discharge curve of the HC electrode-lithium capacitor with lithium pre-embedded under the condition that the ratio of the Activated Carbon (AC) to the Hard Carbon (HC) is 2: 1. In the first figure, the abscissa represents the specific discharge capacity mAh g-1And the ordinate is the voltage value V.
FIG. 2: the charge-discharge curve of the HC electrode-lithium capacitor with lithium pre-embedded under the condition that the ratio of the Activated Carbon (AC) to the Hard Carbon (HC) is 6: 1. In the second graph, the abscissa represents the specific discharge capacity mAh g-1And the ordinate is the voltage value V.
FIG. 3: the charge-discharge curve of the HC electrode-sodium capacitor pre-embedded with sodium is prepared under the condition that the ratio of the Active Carbon (AC) to the Hard Carbon (HC) is 6: 1. In the third diagram, the abscissa represents the specific discharge capacity mAh g-1And the ordinate is the voltage value V.
FIG. 4: the charge-discharge curve of the HC-lithium capacitor without pre-lithium intercalation is carried out. In the fourth diagram, the abscissa represents the specific discharge capacity mAhg-1And the ordinate is the voltage value V.
FIG. 5: charge and discharge curves for graphite-lithium capacitors without pre-intercalation of lithium. In the fifth diagram, the abscissa represents the specific discharge capacity mAh g-1And the ordinate is the voltage value V.
FIG. 6: the pre-lithium-intercalated graphite electrode-lithium capacitor prepared by the invention has a charge-discharge curve. In the sixth graph, the abscissa represents the specific discharge capacity mAh g-1And the ordinate is the voltage value V.
FIG. 7: cycling performance tests were not performed on pre-lithium intercalated graphite-AC capacitors and on pre-lithium intercalated graphite-AC capacitors prepared in accordance with the present invention. In FIG. 7, the abscissa represents the cycle number and the ordinate represents the specific discharge capacity mAh g-1。
The load is the mass (mg cm) of the active carbon or the negative electrode material in each square centimeter of the electrode-2)。
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
Respectively dissolving CMC and SBR in water, stirring until the CMC solution and the SBR solution are completely dissolved to obtain a CMC solution with the mass fraction of 2% and an SBR solution with the mass fraction of 40%, adding an AC, a Super P, a CMC aqueous solution and water into a weighing bottle according to the ratio of AC to Super P to CMC to SBR of 85:9:2:4, adjusting the solid content of the slurry to 34%, wherein the mass of the AC is 0.85g, the mass of the Super P is 0.09g, the mass of the 2% CMC solution is 1g, the mass of the water is 0.78g, stirring for 5h to obtain a uniform slurry, then adding 0.1g of the 40% SBR aqueous solution, stirring uniformly, blade-coating an electrode on an aluminum foil, drying for 12h at 60 ℃, and cutting into a wafer with the diameter of 14mm to obtain the AC electrode.
Respectively dissolving CMC and SBR in water, stirring until the CMC solution and the SBR solution are completely dissolved to obtain a CMC solution with the mass fraction of 2% and an SBR solution with the mass fraction of 40%, adding HC, Super P, CMC aqueous solution and water into a weighing bottle according to the proportion of HC to Super P to CMC to SBR of 85:9:2:4, adjusting the solid content of the slurry to 34%, wherein the HC mass is 0.85g, the Super P mass is 0.09g, the 2% CMC solution mass is 1g, the water mass is 0.78g, stirring for 5h to obtain uniform slurry, then adding 0.1g of 40% SBR aqueous solution, stirring uniformly, blade-coating an electrode on a copper foil, drying for 12h at 60 ℃, and cutting into a wafer with the diameter of 14mm to obtain the HC electrode.
Using an AC electrode with the mass of active carbon of 2mg per square centimeter of the electrode as a positive electrode, 2 lithium sheets with the diameter of 16mm and the thickness of 0.7mm as a negative electrode, and clegard2325 as a diaphragm, using commercial lithium electrolyte and using LiPF as solute6The solvent is a mixed solution of EC: DEC ═ 1:1, and the capacitor is assembled. And standing for 3 hours, performing 0.2mA constant current charging with the cut-off voltage of 4.0V, performing 0.2mA constant current discharging with the cut-off voltage of 1.5V, disassembling the battery after discharging, taking out an AC electrode, and assembling the capacitor by using the same diaphragm and electrolyte and an HC electrode with the mass of 1mg of hard carbon in each square centimeter of electrode. Standing for 0.5h, and then performing 0.2mA constant current charging with the cut-off voltage of 4.0V. And finishing the lithium intercalation process to obtain the pre-intercalated lithium HC-AC capacitor. And testing the first-circle efficiency of the pre-lithiated HC electrode for detecting the pre-lithium intercalation result, disassembling the battery, taking out the HC electrode, and performing 0.2mA constant-current charging and discharging test on the assembled capacitor of the lithium sheet, wherein the voltage range is 0-2V. The results are shown in FIG. 1.
Example 2
Electricity was prepared in the same manner as in example 1, using an AC electrode having a mass of 6mg of activated carbon per square centimeter of electrode as a positive electrode, 2 lithium sheets having a diameter of 16mm and a thickness of 0.7mm as a negative electrode, and a clegard2325 as a separator, and a commercial lithium electrolyte, a mixed solution of LiPF6 as a solute and EC: DEC: 1 as a solvent, to assemble a capacitor. And standing for 3 hours, performing 0.2mA constant current charging with the cut-off voltage of 4.0V, performing 0.2mA constant current discharging with the cut-off voltage of 1.5V, disassembling the battery after discharging, taking out an AC electrode, and assembling the capacitor by using the same diaphragm and electrolyte and an HC electrode with the mass of 1mg of hard carbon in each square centimeter of electrode. Standing for 0.5h, and then performing 0.2mA constant current charging with the cut-off voltage of 4.0V. And finishing the lithium intercalation process to obtain the pre-intercalated lithium HC-AC capacitor. And testing the first-circle efficiency of the pre-lithiated HC electrode for detecting the pre-lithium intercalation result, disassembling the battery, taking out the HC electrode, and performing 0.2mA constant-current charging and discharging test on the assembled capacitor of the lithium sheet, wherein the voltage range is 0-2V. The results are shown in FIG. 2.
Example 3
An electrode was prepared in the same manner as in example 1, using an AC electrode having a mass of 6mg of activated carbon per square centimeter of the electrode as a positive electrode, a metallic sodium as a negative electrode, a glass fiber membrane as a separator, and a sodium ion battery electrolyte solution as a solute, NaClO4The solvent is a mixed solution of EC: DEC ═ 1:1, and the capacitor is assembled. And standing for 3 hours, performing 0.2mA constant current charging with the cut-off voltage of 4.0V, performing 0.2mA constant current discharging with the cut-off voltage of 1.5V, disassembling the battery after discharging, taking out an AC electrode, and assembling the capacitor by using the same diaphragm and electrolyte and an HC electrode with the mass of 1mg of hard carbon in each square centimeter of electrode. Standing for 0.5h, and then performing 0.2mA constant current charging with the cut-off voltage of 4.0V. And finishing the sodium insertion process to obtain the pre-sodium-inserted HC-AC capacitor. And testing the first-circle efficiency of the HC electrode for detecting the pre-sodium-embedding result, disassembling the battery, taking out the HC electrode, and performing 0.2mA constant-current charge-discharge test on the capacitor assembled by the sodium sheet, wherein the voltage range is 0-2.5V. The results are shown in FIG. 3.
Example 4
A graphite electrode was prepared in the same manner as in example 1, using graphite as an active material in an electrode ratio of 90:7:1:2 graphite Super P: CMC: SBR. Using an AC electrode with the mass of active carbon of 6mg per square centimeter of the electrode as a positive electrode, 2 lithium sheets with the diameter of 16mm and the thickness of 0.7mm as a negative electrode, and clegard2325 as a diaphragm, using commercial lithium electrolyte and using LiPF as solute6The solvent is a mixed solution of EC: DEC ═ 1:1, and the capacitor is assembled. And standing for 3 hours, performing 0.2mA constant current charging with the cut-off voltage of 4.0V, performing 0.2mA constant current discharging with the cut-off voltage of 1.5V, disassembling the battery after discharging, taking out the AC electrode, and assembling the capacitor by using the same diaphragm and electrolyte and a graphite electrode with the graphite mass of 4.5mg in each square centimeter of electrode. Standing for 0.5h, and then performing 0.4mA constant current charging with the cut-off voltage of 4.0V. And finishing the lithium intercalation process to obtain the pre-intercalated lithium graphite-AC capacitor. And testing the first-circle efficiency of the pre-lithiated graphite electrode for detecting the pre-lithium intercalation result, disassembling the battery, taking out the graphite electrode, and carrying out 0.4mA constant current charging and discharging test on the assembled capacitor of the graphite electrode and a lithium sheet, wherein the voltage range is 0-1.5V. The results are shown in FIG. 6.
Example 5
Electrodes were prepared in the same manner as in examples 1 and 4, using an AC electrode having an activated carbon mass of 6mg per square centimeter of the electrode as the positive electrode, 2 lithium sheets having a diameter of 16mm and a thickness of 0.7mm as the negative electrode, and clegard2325 as the separator, using a commercial lithium electrolyte, and a solute of LiPF6The solvent is a mixed solution of EC: DEC ═ 1:1, and the capacitor is assembled. And standing for 3 hours, performing 0.2mA constant current charging with the cut-off voltage of 4.0V, performing 0.2mA constant current discharging with the cut-off voltage of 1.5V, disassembling the battery after discharging, taking out the AC electrode, and assembling the capacitor by using the same diaphragm and electrolyte and a graphite electrode with the graphite mass of 4.8mg in each square centimeter of electrode. Standing for 0.5h, and then performing 0.4mA constant current charging with the cut-off voltage of 4.0V. And finishing the lithium intercalation process to obtain the pre-intercalated lithium graphite-AC capacitor. And carrying out 0.3mA constant current circulation test on the capacitor, wherein the voltage range is 2.0V-4.0V. The results are shown in FIG. 7.
Comparative example 1
The electrode was prepared in the same manner as in example 1, and the HC electrode first-pass efficiency was directly tested without performing the pre-lithium intercalation process. Using an HC electrode with the mass of hard carbon in each square centimeter of the electrode as a positive electrode, 2 lithium sheets with the diameter of 16mm and the thickness of 0.7mm as a negative electrode, and clegard2325 as a diaphragm, using a commercial lithium electrolyte, and using LiPF as a solute6The solvent is a mixed solution of EC and DEC which is 1:1, and the mixed solution is assembled into a capacitor to be subjected to 0.2mA constant current charging and discharging test, wherein the voltage range is 0-2V. The results are shown in FIG. 4.
Comparative example 2
The same method as in example 4 was used to prepare electrodes, and the first-turn efficiency of the graphite electrode was directly tested without a pre-lithium intercalation process. Taking a graphite electrode with the graphite mass of 4.5mg in each square centimeter of the electrode as a positive electrode, 2 lithium sheets with the diameter of 16mm and the thickness of 0.7mm as a negative electrode, and clegard2325 as a diaphragm, using commercial lithium electrolyte and taking LiPF as solute6The solvent is a mixed solution of EC and DEC which is 1:1, and the mixed solution is assembled into a capacitor to be subjected to 0.4mA constant current charging and discharging test, wherein the voltage range is 0-1.5V. The results are shown in FIG. 5.
Comparative example 3
Electrodes were prepared in the same manner as in examples 1 and 4 without preliminary treatmentThe graphite-AC capacitor is directly assembled in the lithium embedding process, an AC electrode with the mass of 6mg of active carbon in each square centimeter of electrode is taken as a positive electrode, a graphite electrode with the mass of 4.8mg of graphite in each square centimeter of electrode is taken as a negative electrode, clegard2325 is taken as a diaphragm, commercial lithium electrolyte is used, and LiPF is used as solute6And the solvent is a mixed solution of EC: DEC ═ 1:1, so as to obtain the graphite-AC capacitor without lithium intercalation. And carrying out 0.3mA constant current circulation test on the capacitor, wherein the voltage range is 2.0V-4.0V. The results are shown in FIG. 7.
Evaluation of results of examples
Table 1: first pass efficiency of different electrode samples
To test the prelithiation effect, the prelithiated negative electrode was taken out and assembled with a metal material to form a capacitor to test the first cycle efficiency, comparative example 1 was a sample of a hard carbon electrode without prelithiation, examples 1 and 2 were samples of a hard carbon electrode with different activated carbon/hard carbon loading ratios with lithium intercalation, and example 3 was a sample of a hard carbon electrode with sodium intercalation. It can be seen through the comparison that the efficiency of the first circle of the hard carbon electrode after pre-embedding lithium is obviously higher than that of a sample without pre-embedding lithium, the pre-embedding lithium degree can be controlled by the load ratio of the activated carbon and the hard carbon, the higher activated carbon load can increase the amount of adsorbing metal ions, the pre-embedding lithium degree is higher, meanwhile, the cut-off voltage of the discharge of the metal-activated carbon capacitor can also increase the adsorption amount of the metal ions, and the conditions can be regulated according to actual requirements, so that different application requirements can be easily met. The results of example 3 illustrate that the process described in the present invention is equally applicable to the pre-intercalation of other metals such as sodium. The comparison example 2 is a graphite electrode without pre-intercalated lithium, the example 4 is a graphite electrode with pre-intercalated lithium, the first-turn efficiency of the graphite electrode with pre-intercalated lithium is obviously higher than that of the graphite electrode without pre-intercalated lithium, and the method described by the invention is suitable for negative electrodes with pre-intercalated metals such as hard carbon, graphite and the like. Comparative example 3 is a graphite-AC capacitor without pre-intercalation of lithium and example 5 is a graphite-AC capacitor with pre-intercalation of lithium, the specific discharge capacity of the graphite-AC capacitor with pre-intercalation of lithium being significantly higher than that of the graphite-AC capacitor without pre-intercalation of lithium, confirming that the working potential of the negative electrode is reduced by metal pre-intercalation, thereby increasing the specific discharge capacity of the capacitor. The data prove that the technology of pre-embedding the negative metal by using the double electric layers can realize more sufficient pre-embedding of the negative metal, the irreversible capacity and the working potential of the negative electrode are obviously reduced, the process is simple, the pre-embedding amount of the metal is easy to regulate and control, and the stability and the safety of the active carbon electrode which is disassembled in the middle process and adsorbs the metal ions are better, so that the active carbon electrode has higher practical value.
Claims (10)
1. A preparation method of a super capacitor is characterized by comprising the following steps: a metal material is used as a negative electrode, an activated carbon electrode is used as a positive electrode to assemble a metal-activated carbon capacitor, and the activated carbon electrode with a metal ion adsorption layer is obtained after discharging; and then the activated carbon electrode adsorbing the metal ion layer is used as an anode and is assembled with a to-be-metal pre-embedded cathode to form an activated carbon-to-be-metal pre-embedded cathode capacitor, charging is carried out to realize metal pre-embedding of the cathode, and finally the super capacitor with the metal pre-embedded electrode as the cathode and the activated carbon electrode as the anode is obtained.
2. The method of claim 1, further comprising: the active carbon electrode or the to-be-metal pre-embedded negative electrode is prepared by the following steps:
(1) dissolving organic polymer resin in an organic solvent or water, and stirring for 0.5-2 hours at the temperature of 20-100 ℃ to form a corresponding polymer solution;
(2) adding a conductive agent and a positive electrode active substance or a negative electrode active substance into the solution, and fully stirring for 2-10 hours at the temperature of 20-50 ℃ to finally prepare a blending solution; wherein the solid content is 5-40 wt%;
the anode active substance is active carbon, and the cathode active substance is one or more than two of hard carbon, soft carbon, graphite, silicon-carbon composite material, silicon monoxide and tin-based material;
(3) scraping the blended solution obtained in the step (2) on an aluminum foil to form a whole, and drying for 2-48 h to obtain a finished product of an activated carbon electrode or a to-be-metal pre-embedded negative electrode;
the organic solvent is one or more than two of DMSO, DMAC, NMP and DMF.
3. The method of claim 2, further comprising: the active material loading in the active carbon electrode or the to-be-metal pre-embedded negative electrode is 1mg cm-3～10mg cm-3Wherein the ratio of the positive electrode active material to the negative electrode active material is 1: 1-10: 1, preferably 2: 1-6: 1.
4. the method of claim 2, further comprising: the mass of the organic polymer resin in the active carbon electrode or the to-be-metal pre-embedded negative electrode accounts for 3-60 wt% of the total mass of the electrode; the conductive agent accounts for 5-20 wt% of the total mass of the electrode;
the active carbon or the negative electrode material accounts for 30-90 wt% of the whole electrode.
5. The method according to claim 2 or 4, wherein: the organic polymer resin is Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylpyrrolidone (PVP), Polystyrene (PS), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), Polyethersulfone (PES), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), sodium carboxymethylcellulose
(CMC) and Styrene Butadiene Rubber (SBR); the conductive agent is one or more than two of commercialized carbon nano-tube, graphene, carbon nano-fiber, BP2000, KB600, KB300, XC-72, Super-P, acetylene black and active carbon.
6. The method according to claim 1 or 2, wherein: the metal material is one or more than two of metal simple substances or salts capable of releasing metal ions, and the metal is one or more than two of lithium, sodium, magnesium and potassium; the salt capable of releasing metal ions is one or more of LiMO (M ═ one or more of Co, Ni, Fe, Cu and Mn);
the active carbon material is one or more than two mixed materials of active carbon or active carbon and lithium ion battery anode material LiMO (one or more than two of Co, Ni, Fe, Cu and Mn).
7. The method of claim 1, further comprising: the cut-off voltage of the metal-activated carbon capacitor in the discharging process is 0V to any value less than the initial voltage of the capacitor, and preferably 1.5V.
8. The method of claim 1, further comprising:
in the charging process of the activated carbon-to-be-metal pre-embedded negative electrode capacitor, the initial voltage is used as the initial voltage, and the cut-off voltage is any value from the initial voltage of the capacitor to 4.3V, preferably 4.0V.
9. The method of claim 1, further comprising: the electrolyte adopted by the capacitor adopts EC: DEC 1:1 solvent and LiPF solute6、NaClO4Or KPF6One kind of (1).
10. A supercapacitor made by the process of any one of claims 1 to 9.
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