CN108074750B - Double-ion capacitor battery - Google Patents
Double-ion capacitor battery Download PDFInfo
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- CN108074750B CN108074750B CN201610984193.8A CN201610984193A CN108074750B CN 108074750 B CN108074750 B CN 108074750B CN 201610984193 A CN201610984193 A CN 201610984193A CN 108074750 B CN108074750 B CN 108074750B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- 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
Abstract
The invention relates to a dual-ion capacitor battery. The invention relates to a dual-ion capacitor battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein an active material of the positive electrode is a carbon material; the surface of the positive electrode forms an electric double layer capacitor. The dual-ion capacitor battery provided by the invention effectively solves the problems of poor coulombic efficiency and poor cycle stability, and has higher energy density compared with a dual-ion battery and a super capacitor.
Description
Technical Field
The invention relates to a dual-ion capacitor battery.
Background
In recent years, due to the large-scale commercial application of lithium ion batteries, the storage amount of lithium on the earth is less and less, and the price of lithium is bound to be in an increasing trend, so that the cost of the double-ion battery is lower compared with that of the lithium ion battery.
In the case of a double-graphite battery in which both the positive and negative electrode materials are made of graphite, the electrolyte salt is LiPF6. Li in the electrolyte when the battery is charged+Ions migrate to the negative electrode and are embedded in the negative electrode graphite, PF6 -Ions migrate to the positive electrode and are embedded into the positive electrode graphite; when the battery discharges, the anions and the cations embedded in the positive electrode and the negative electrode return to the electrolyte again to realize circulation.
Compared with the traditional lithium ion battery, the dual-ion battery has higher charge and discharge voltage, although the positive electrode and the negative electrode of the dual-ion battery both adopt graphite carbon materials, the cost of the battery is effectively reduced. However, the current bi-ion battery has low coulombic efficiency and poor cycle stability, and the main reason is that PF (positive electrode Filter)6 -Ion ratio to Li+The ions have a larger spatial size and are therefore difficult to fully intercalate into the graphite lattice when the battery is charged; PF (particle Filter)6 -The state of ions in the positive electrode material is that a part of ions are embedded in the graphite lattice, and a large amount of PF is left6 -The ions are only adsorbed on the surface of the positive electrode material, and the PF adsorbed on the surface of the positive electrode material is formed after the charging is stopped6 -The ions are returned to the electrolyte again. This causes a decrease in the battery discharge capacity and a situation in which the lithium ions of the negative electrode are accumulated more and more. Meanwhile, after a plurality of charge-discharge cycles, the battery shows the problems of increased internal resistance, serious capacity attenuation and the like.
Modification research on the bi-ion battery mainly focuses on the direction of the carbon anode, and the carbon anode material embedded with anions directly determines the cycle stability of the bi-ion battery. The ideal carbon cathode material of the bi-ion battery is to ensure the stable intercalation and de-intercalation of anions and have higher anion storage capacity, but the bi-ion battery cathode material which completely meets the requirements is not available at present. The large amount of anions can cause the graphite layer of the carbon cathode material to fall off and the structure to collapse, thereby causing the irreversible loss of the battery capacity. Anions in the bi-ion battery can only be partially embedded into the carbon anode material, and the specific capacity of the carbon anode material directly influences the energy density of the bi-ion battery, which is another problem in the current bi-ion battery carbon anode material.
Meanwhile, in the bi-ion battery, due to the fact that the anion size is large and is difficult to be embedded into the graphite lattice, a series of problems such as low coulombic efficiency, poor cycle stability, limited charge-discharge specific capacity and the like do not have an effective solution at present, and the problems are also key points of the bi-ion battery in practical application.
Disclosure of Invention
In order to solve the problems, the invention provides a dual-ion capacitor battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the active material of the positive electrode is a carbon material; the surface of the positive electrode forms an electric double layer capacitor. In the present invention, the positive electrode provides a site for anion intercalation.
The novel dual-ion capacitor battery of the invention is characterized in that the dual-ion battery has the characteristics of a super capacitor at the same time through the special design of a positive electrode material or the design of mixing a material with large specific surface area, such as capacitive activated carbon, into an electrode material on the basis of energy storage of the dual-ion battery, thereby realizing the effect of the super capacitorThe double electric layers of the existing battery store energy physically and store energy by reversible Faraday chemical reaction. For example, a double-ion capacitor battery with graphite and active carbon as positive electrodes and graphite as a negative electrode obtains negative charges of electrons when the battery is charged, and Li with positive charges in electrolyte+Migrate to the negative electrode and are embedded into the negative electrode graphite, while the positive electrode loses the positive charge of electrons, and the PF with negative charge in the electrolyte6 -Ions migrate to the positive electrode and become partially embedded in the positive electrode graphite material due to PF6 -The positive charge of the positive electrode material cannot be completely neutralized and still has surplus positive charge, and the characteristic that the active carbon in the positive electrode material has large specific surface area is utilized to partially charge the negative PF6 -The ions are adsorbed on the surface of the positive electrode material to form a stable electric double layer with the excessive positive charges, so that electric double layer energy storage is realized (see fig. 1). The formation of the double electric layers avoids the irreversible capacity attenuation caused by graphite layer exfoliation and structure collapse due to excessive anion intercalation in the positive electrode graphite.
The special design of the anode material needs to realize the stable adsorption effect on partial anions which are not embedded into the anode, so that materials with adsorption capacity such as activated carbon can be selected to be added into the anode, and the anode can be designed to be a material with large specific surface area.
The energy storage mode of the double-ion capacitor battery belongs to asymmetric energy storage, the energy storage is realized by embedding positive ions in a negative electrode, and the energy storage is realized by embedding negative ions in a positive electrode and forming a double electric layer on the surface of the positive electrode.
As an embodiment, the specific surface area of the carbon material is 100m2/g～4000m2(ii)/g; the porosity of the carbon material is 0.1cm3/g～10cm3(ii)/g; preferably, the specific surface area of the carbon material is 1000m2/g～2200m2(ii)/g; the porosity of the carbon material is 0.2cm3/g～5cm3(ii) in terms of/g. The invention combines the dual-ion battery and the super capacitor, so that the dual-ion capacitor battery prepared by the invention has excellent energy storagePerformance and cycle performance. The design of the double-ion battery, particularly the increase of the anion embedding amount, ensures that the super capacitor obtains excellent energy storage capacity; the design of the double electric layers of the positive electrode ensures that the dual-ion hybrid capacitor battery obtains excellent cycle performance. Therefore, the carbon material with high specific surface area and high porosity can be beneficial to the embedding of anions, and simultaneously improves the energy storage capacity of the electric double layer of the double-ion capacitor battery, and further improves the cycle stability and the coulombic efficiency of the double-ion capacitor battery.
In one embodiment, the carbon material is at least one selected from the group consisting of activated carbon, porous carbon, carbon nanotubes, graphite foam, graphene, and mesocarbon microbeads; preferably, the carbon material is graphite foam and/or graphene. The carbon material selected by the invention has a structure with high specific surface area and high porosity, so that the carbon material has certain capacitance energy storage characteristics, namely, an electric double layer capacitor is formed, and stable embedding of anions can be realized.
The invention also provides a dual-ion capacitor battery, wherein the carbon material comprises at least one selected from natural graphite, foam graphite, mesocarbon microbeads and graphene and a mixture of activated carbon; preferably, the carbon material includes natural graphite and activated carbon.
The cathode material disclosed by the invention can realize stable embedding of anions and can form a stable double electric layer capacitor on the surface of the material. Taking a dual-ion capacitor battery using graphite and activated carbon as a positive electrode as an example, however, this should not be understood as a limitation to the present invention, when the dual-ion capacitor battery using graphite and activated carbon as a positive electrode is charged, anions in the electrolyte migrate to the positive electrode, a part of anions are embedded into the crystal lattice of the graphite material to realize chemical energy storage, and another part of anions form a stable double electric layer on the surface of the activated carbon of the positive electrode to realize electric double layer energy storage; when the battery is discharged, the anions embedded in the graphite crystal lattice and the anions forming an electric double layer on the surface are returned to the electrolyte again to realize the circulation of the battery.
In one embodiment, the mass of the activated carbon is 5% to 80% of the mass of the carbon material; preferably, the mass of the activated carbon is 20% to 50% of the mass of the carbon material. In the invention, the activated carbon is added to provide a large specific surface area to realize double-layer energy storage, and another component in the active material, such as graphite, realizes anion intercalation energy storage. If the amount of the activated carbon is too small, the function of storing redundant anions in the positive electrode cannot be completely realized, and meanwhile, the problems that the graphite structure is unstable and the battery capacity is irreversibly attenuated due to excessive intercalation of the anions in the graphite are caused. If the amount of the activated carbon is excessive, the energy storage capacity of the embedded anions in the graphite is far higher than the energy storage capacity of the double electric layers of the activated carbon, so that the content of the graphite is reduced, and the specific capacity of the positive active material is indirectly reduced. Therefore, the content of the activated carbon is preferably ensured to obtain the technical effect of the double-ion capacitor battery.
In one embodiment, the active material of the negative electrode is at least one selected from the group consisting of a metal, an alloy, a metal oxide, and graphite.
In one embodiment, the separator is selected from a ceramic separator, a glass microfiber separator, a polymer separator, or a non-woven fabric separator.
As an embodiment, the electrolyte includes a lithium salt selected from LiFP6(Lithiumhexafluorophosphate)、LiTFSI(Lithium bis(trifluoromethylsulfonyl)imide)、LiClO4(Lithium perchlorate)、LiFSI(Lithium bis(fluorosulfonyl)imide)、LiFNFSI(lithium(fluorosulfonyl)-(nonafluorobutanesulfonyl)imide)、LiSAB(lithiumsalicylatoborate)、LiTADC(lithium1,2,3-triazole-4,5-dicarbonitrile)、LiAsF6(Lithium hexafluoroarsenate)、LiBETI(lithium bis-(pentafluoroethanesulfonyl)imide)、LiBOB(lithium bis(oxalato)borate)、LiTOP(lithium Tristan(oxalato)phophate)、LiTFOP(lithium tetrafluorooxalatophosphate)、LiTFBP(tris[3-fluoro-1,2-benzenediolato(2-)-O,O′]phosphate)、LiTBP(lithium tris[1,2-benzenediolato(2-)-O,O′]phosphate)、LiFAB(lithium pentafluoroethyltrifluoroborate)、LiMOB(lithium(malonatooxalato)borate)、LIDFOB(lithium difluorooxalatoborate)、Li2DFB(dilithium dodecafluoro dodecaborate)、Li2B12F12(dilithiumdodecafluorododecaborate)、LiB(CN)4(tetracyanoborate) and LiBF4(Lithiumtetrafluoroborate). Preferably, the lithium salt is selected from LiPF6、LiTFSI、LiBETI、LiClO4At least one of LiBOB and LiTSI. The lithium salt not only plays a role of an ion conductor, but also more importantly provides anions and cations required by the anode and the cathode.
In one embodiment, the lithium salt concentration is 1mol/L to 12 mol/L; preferably, the lithium salt concentration is 4mol/L to 8 mol/L. In the double-ion capacitor battery, the negative electrode realizes the intercalation energy storage of cations, and the positive electrode realizes the intercalation of anions and the formation of double electric layer energy storage. Therefore, the concentration of the lithium salt cannot be too low, and the higher concentration of the lithium salt can reduce the using amount of the electrolyte and reduce the total mass of the battery, thereby indirectly improving the energy density of the battery; however, when the concentration of the lithium salt is too high, the lithium salt cannot be completely dissolved, and the electrolyte is viscous and has low ionic conductivity, thereby affecting the rate performance of the battery. The preferred lithium salt concentration of the present invention ensures that better results are obtained.
As an embodiment, the electrolyte includes an organic solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl ether (DME), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Acetate (EA), Methyl Propionate (MP), Ethyl Propionate (EP), Methyl Butyrate (MB), Ethyl Butyrate (EB), Propyl Butyrate (PB), Butyl Butyrate (BB), Methyl Formate (MF), Ethyl Formate (EF), Methyl Difluoroacetate (MDF), sulfolane (TMS), Ethyl Methane Sulfonate (EMS), Butyl Sulfone (BS), Ethyl Vinyl Sulfone (EVS), and Ethylene Carbonate (EC).
In one embodiment, the charge cut-off voltage of the dual-ion capacitor battery is 3V-5V; the discharge cut-off voltage of the double-ion hybrid super capacitor is 1V-3V. The working temperature of the dual-ion capacitor battery is-40 ℃ to 80 ℃.
Another object of the present invention is to provide a method for preparing a dual-ion capacitor battery, comprising the following steps:
a) mixing and coating the positive electrode material on a positive electrode current collector, and drying to form a positive electrode plate; the positive electrode material comprises a carbon material, a conductive agent and a binder;
b) coating the negative electrode material on a negative electrode current collector in a mixed manner, and drying to form a negative electrode piece; the negative electrode material comprises an active material of a negative electrode, a conductive agent and a binder;
c) and assembling the positive plate, the negative plate, the diaphragm and the electrolyte to obtain the dual-ion capacitor battery.
In one embodiment, the mass of the carbon material is 80% to 95% of the total mass of the positive electrode material; the mass of the active material of the negative electrode is 80-95% of the total mass of the negative electrode material.
As an embodiment, the temperature of the drying treatment is 60 ℃ to 200 ℃; as a preference; the temperature of the drying treatment is 80-150 ℃.
In one embodiment, the binder is at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and carboxymethylcellulose (CMC); preferably, the binder is PVDF. The mass of the binder is 5-15% of the total mass of the positive electrode material; preferably, the mass of the binder is 5% to 8% of the total mass of the positive electrode material.
In one embodiment, the conductive agent is at least one of superconducting carbon black, acetylene black, graphene, VGCF, and carbon nanotubes; preferably, the conductive agent is superconducting carbon black and/or graphene. The conductive agent accounts for 2-10% of the total mass of the positive electrode material; preferably, the content of the conductive agent in the total mass of the cathode material is 3-8%.
The double-ion capacitor battery provided by the invention not only ensures the stable embedding of anions in the anode material, but also enables the anions gathered on the surface of the anode to form stable double-electric-layer energy storage. Compared with the traditional double-ion battery, the double-ion capacitor battery provided by the invention effectively solves the problems of low coulombic efficiency and poor cycle stability, and has higher energy density compared with the double-ion battery and a super capacitor.
Drawings
FIG. 1: the invention is a schematic diagram of a charging process of a dual-ion capacitor battery;
FIG. 2: a schematic diagram of the charge-discharge cycle performance of example 3 of the present invention;
FIG. 3: a schematic diagram of charging and discharging coulombic efficiency of embodiment 3 of the invention;
FIG. 4: a charge and discharge plateau of embodiment 3 of the present invention.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
Example 1:
the first step is as follows: mixing natural graphite, graphene and PVDF binder (PVDF is dissolved in NMP and has the concentration of 1% by weight) according to the weight ratio of 7: 2: 1, mixing the mixture evenly, pulping, coating the mixture on an aluminum net and drying the mixture to obtain the positive plate.
The second step is that: mixing mesocarbon microbeads, conductive carbon black and a PVDF binder (PVDF is dissolved in NMP and the concentration is 1 percent by weight) according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping, coating the mixture on an aluminum foil, and drying the aluminum foil to obtain a negative plate.
The third step: the diaphragm adopts a glass microfiber diaphragm, and the electrolyte adopts 4mol/L LiPF6EMC (ethyl methyl carbonate) solution of (c).
The fourth step: and (3) stacking the electrode plates and the diaphragm in a CR2032 type battery case in the order of the positive plate, the diaphragm and the negative plate under the environment of controlling the water oxygen content, injecting a proper amount of electrolyte, and sealing the battery case to obtain the button battery.
The fifth step: and (3) carrying out electrochemical performance test on the button cell, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
Example 2:
the first step is as follows: mixing mesocarbon microbeads, activated carbon and PVDF binder (PVDF is dissolved in NMP and the concentration is 1% by weight) according to the weight ratio of 6: 3: 1, mixing the mixture evenly, pulping, coating the mixture on carbon cloth, and drying the carbon cloth to obtain the positive plate.
The second step is that: mixing natural graphite, conductive carbon black and PVDF binder (PVDF is dissolved in NMP and has the concentration of 1 wt%) according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping, coating the mixture on an aluminum foil, and drying the aluminum foil to obtain a negative plate.
The third step: the diaphragm adopts a PP polymer diaphragm, and the electrolyte adopts 2mol/L LiTFSI methyl ethyl carbonate (EMC) solution.
The fourth step: and overlapping the electrode plate and the diaphragm in the aluminum plastic film in the order of the positive plate, the diaphragm and the negative plate under the environment of controlling the water oxygen content, injecting a proper amount of electrolyte, and sealing the aluminum plastic film to obtain the small soft package battery.
The fifth step: and (3) carrying out electrochemical performance test on the small soft package battery, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
Example 3:
the first step is as follows: mixing natural graphite, activated carbon and PTFE binder (PTFE is dissolved in deionized water, and the concentration is 40 percent by weight) according to a ratio of 4: 4: 2, mixing the mixture evenly, pulping, coating the mixture on foamed nickel, and drying the foamed nickel to obtain the positive plate.
The second step is that: the metal aluminum foil is directly used as the negative plate.
The third step: the diaphragm adopts a glass microfiber diaphragm, and the electrolyte adopts 6mol/L LiPF6Ethyl Methyl Carbonate (EMC) solution.
The fourth step: same as in example 1
The fifth step: and (3) carrying out electrochemical performance test on the button cell, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
The test results of example 3 are shown in fig. 2 and fig. 3, wherein constant current charging and discharging is adopted, the charging and discharging voltage interval is 3-5V, and the charging and discharging multiplying power is 0.5C.
Example 4:
the first step is as follows: natural graphite, carbon foam, PTFE binder (PTFE dissolved in deionized water at 20% wt) was mixed in a 6: 3: 1, mixing the mixture evenly, pulping, coating the mixture on foamed nickel, and drying the foamed nickel to obtain the positive plate.
The second step is that: mo is mixed with6S8Conductive carbon black, PTFE binder (PTFE dissolved in deionized water at 20% wt) as 8: 1: 1, mixing the mixture evenly, pulping the mixture, coating the mixture on foamed nickel, and drying the foamed nickel to obtain a negative plate.
The third step: the diaphragm adopts a porous ceramic diaphragm, and the electrolyte adopts 10mol/L of LiTFSI deionized water solution.
The fourth step: same as in example 1
The fifth step: and (3) carrying out electrochemical performance test on the button cell, wherein the voltage interval of the charge and discharge test is 1.5-3.4V, and the specific test result is shown in table 1.
Example 5:
the first step is as follows: the graphite foam, the conductive carbon black and the PVDF binder (PVDF dissolved in NMP at a concentration of 1% by weight) were mixed in a ratio of 8: 1: 1, mixing the mixture evenly, pulping, coating the mixture on carbon cloth, and drying the carbon cloth to obtain the positive plate.
The second step is that: the metal aluminum foil is directly used as the negative plate.
The third step: the diaphragm adopts a PP polymer diaphragm, and the electrolyte adopts 2mol/L LiTFSI methyl ethyl carbonate (EMC) solution.
The fourth step: and overlapping the electrode plate and the diaphragm in the aluminum plastic film in the order of the positive plate, the diaphragm and the negative plate under the environment of controlling the water oxygen content, injecting a proper amount of electrolyte, and sealing the aluminum plastic film to obtain the small soft package battery.
The fifth step: and (3) carrying out electrochemical performance test on the small soft package battery, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
Example 6:
the first step is as follows: mixing natural graphite, activated carbon and PTFE binder (PTFE is dissolved in deionized water, and the concentration is 40 percent by weight) according to the weight ratio of 2: 6: 2, mixing the mixture evenly, pulping, coating the mixture on foamed nickel, and drying the foamed nickel to obtain the positive plate.
The second step is that: lithium titanate, conductive carbon black and PTFE binder (PTFE is dissolved in deionized water, and the concentration is 20 wt%) are mixed according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping the mixture, coating the mixture on foamed nickel, and drying the foamed nickel to obtain a negative plate.
The third step: the diaphragm adopts a glass microfiber diaphragm, and the electrolyte adopts 4mol/L LiPF6Ethyl Methyl Carbonate (EMC) solution.
The fourth step: same as in example 1
The fifth step: and (3) carrying out electrochemical performance test on the button cell, wherein the voltage interval of the charge and discharge test is 1.5-3.4V, and the specific test result is shown in table 1.
Example 7:
the first step is as follows: mixing natural graphite, activated carbon and PTFE binder (PTFE is dissolved in deionized water, and the concentration is 40 percent by weight) according to the weight ratio of 1: 3: 1, mixing the mixture evenly, pulping, coating the mixture on foamed nickel, and drying the foamed nickel to obtain the positive plate.
The second step is that: lithium titanate, conductive carbon black and PTFE binder (PTFE is dissolved in deionized water, and the concentration is 20 wt%) are mixed according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping the mixture, coating the mixture on foamed nickel, and drying the foamed nickel to obtain a negative plate.
The third step: the diaphragm adopts a glass microfiber diaphragm, and the electrolyte adopts 1mol/L LiBETI diethyl carbonate (DEC) solution.
The fourth step: same as in example 1
The fifth step: and (3) carrying out electrochemical performance test on the button cell, wherein the voltage interval of the charge and discharge test is 1.5-3.4V, and the specific test result is shown in table 1.
Example 8:
the first step is as follows: the mesocarbon microbeads, activated carbon, PVDF binder (PVDF dissolved in NMP at 1% wt) were mixed in a ratio of 0.5: 8.5: 1, mixing the mixture evenly, pulping, coating the mixture on carbon cloth, and drying the carbon cloth to obtain the positive plate.
The second step is that: mixing natural graphite, conductive carbon black and PVDF binder (PVDF is dissolved in NMP and has the concentration of 1 wt%) according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping, coating the mixture on an aluminum foil, and drying the aluminum foil to obtain a negative plate.
The third step: the diaphragm adopts a PP polymer diaphragm, and the electrolyte adopts 2mol/L LiTFSI methyl ethyl carbonate (EMC) solution.
The fourth step: and overlapping the electrode plate and the diaphragm in the aluminum plastic film in the order of the positive plate, the diaphragm and the negative plate under the environment of controlling the water oxygen content, injecting a proper amount of electrolyte, and sealing the aluminum plastic film to obtain the small soft package battery.
The fifth step: and (3) carrying out electrochemical performance test on the small soft package battery, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
Example 9:
the first step is as follows: mixing mesocarbon microbeads, activated carbon and PVDF binder (PVDF is dissolved in NMP and the concentration is 1% by weight) according to the weight ratio of 6: 3: 1, mixing the mixture evenly, pulping, coating the mixture on carbon cloth, and drying the carbon cloth to obtain the positive plate.
The second step is that: mixing natural graphite, conductive carbon black and PVDF binder (PVDF is dissolved in NMP and has the concentration of 1 wt%) according to the weight ratio of 8: 1: 1, mixing the mixture evenly, pulping, coating the mixture on an aluminum foil, and drying the aluminum foil to obtain a negative plate.
The third step: the diaphragm adopts a PP polymer diaphragm, and the electrolyte adopts 0.2mol/L LiTFSI methyl ethyl carbonate (EMC) solution.
The fourth step: and overlapping the electrode plate and the diaphragm in the aluminum plastic film in the order of the positive plate, the diaphragm and the negative plate under the environment of controlling the water oxygen content, injecting a proper amount of electrolyte, and sealing the aluminum plastic film to obtain the small soft package battery.
The fifth step: and (3) carrying out electrochemical performance test on the small soft package battery, wherein the voltage interval of the charge and discharge test is 3-5V, and the specific test result is shown in table 1.
From example 1 and example 8, it can be seen that: when the mixed carbon material of the mesocarbon microbeads and the activated carbon is used as the anode material, the content of the activated carbon reaches 94 percent, and the content of the mesocarbon microbeads is reduced, the specific capacity of the battery is reduced because the energy storage capacity of the mesocarbon microbeads in the mixed carbon material is far higher than the energy storage capacity of the double electric layers of the activated carbon.
From example 1 and example 9, it can be seen that: when the electrolyte adopts 0.2mol/L LiTFSI methyl ethyl carbonate (EMC) solution, namely the concentration of the electrolyte is lower than that of the electrolyte, the lower lithium salt concentration in the electrolyte can not provide sufficient anions and cations to participate in charge-discharge reaction of the battery because the anions and cations embedded in the anode and the cathode in the battery system are provided by the lithium salt in the electrolyte, so that the capacity of the electrode material can not be fully exerted. Thus, the battery of example 9 was reduced in specific discharge capacity as compared with example 1.
TABLE 1
Claims (12)
1. A dual-ion capacitor battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that: the active material of the positive electrode is a carbon material, and the carbon material is graphite foam and graphene; or the carbon material is a mixture of at least one selected from natural graphite, foam graphite and mesocarbon microbeads and activated carbon; the surface of the positive electrode forms an electric double layer capacitor, and the specific surface area of the carbon material is 1000m2/g～4000m2(ii)/g; the porosity of the carbon material is 0.1cm3/g～10cm3/g。
2. The dual-ion capacitor battery of claim 1, wherein: the specific surface area of the carbon material is 1000m2/g～2200m2(ii)/g; the porosity of the carbon material is 0.2cm3/g～5cm3/g。
3. The dual-ion capacitor battery of claim 1, wherein: the carbon material comprises natural graphite and activated carbon.
4. The dual-ion capacitor battery of claim 1, wherein: the mass of the activated carbon is 5-80% of the mass of the carbon material.
5. The dual-ion capacitor battery of claim 4, wherein: the mass of the activated carbon is 20-50% of the mass of the carbon material.
6. The dual-ion capacitor battery of claim 1, wherein: the active material of the negative electrode is at least one selected from the group consisting of metals, alloys, metal oxides, and graphite.
7. The dual-ion capacitor battery of claim 1, wherein: the active material of the negative electrode is selected from mesocarbon microbeads, natural graphite, metallic aluminum and Mo6S8And lithium titanate.
8. The dual-ion capacitor battery of claim 1, wherein: the electrolyte comprises a lithium salt selected from LiFP6、LiTFSI、LiClO4、LiFSI、LiFNFSI、LiSAB、LiTADC、LiAsF6、LiBETI、LiBOB、LiTOP、LiTFOP、LiTFBP、LiTBP、LiFAB、LiMOB、LIDFOB、Li2DFB、Li2B12F12、LiB(CN)4And LiBF4At least one of them.
9. The dual-ion capacitor battery of claim 8, wherein: the lithium salt is selected from LiPF6、LiTFSI、LiBETI、LiClO4At least one of LiBOB and LiTSI.
10. The dual-ion capacitor battery of claim 8, wherein: the concentration of the lithium salt is 1-12 mol/L.
11. The dual-ion capacitor battery of claim 10, wherein: the concentration of the lithium salt is 4-8 mol/L.
12. The dual-ion capacitor battery of claim 1, wherein: the electrolyte contains an organic solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl ether (DME), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Acetate (EA), Methyl Propionate (MP), Ethyl Propionate (EP), Methyl Butyrate (MB), Ethyl Butyrate (EB), Propyl Butyrate (PB), Butyl Butyrate (BB), Methyl Formate (MF), Ethyl Formate (EF), Methyl Difluoroacetate (MDF), sulfolane (TMS), Ethyl Methanesulfonate (EMS), Butyl Sulfone (BS), ethylvinyl sulfone (EVS), and Ethylene Carbonate (EC).
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| CN109887755A (en) * | 2019-02-26 | 2019-06-14 | 清华大学 | A kind of double ion type mixed capacitor and preparation method thereof |
| CN109904444A (en) * | 2019-03-22 | 2019-06-18 | 深圳先进技术研究院 | Lithium titanate battery and its preparation method and application |
| CN112164826A (en) * | 2020-09-29 | 2021-01-01 | 中国科学院长春应用化学研究所 | Low-temperature electrolyte of double-ion battery and double-ion battery |
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| JP2008294314A (en) * | 2007-05-28 | 2008-12-04 | Sanyo Electric Co Ltd | Capacitor |
| CN102820136A (en) * | 2012-08-14 | 2012-12-12 | 江苏捷峰高科能源材料股份有限公司 | High-energy-density supercapacitor |
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| CN104600353A (en) * | 2013-11-01 | 2015-05-06 | 微宏动力系统（湖州）有限公司 | Anion-cation double intercalated battery |
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