WO2022088610A1 - Lithium-ion capacitor, manufacturing method for same, and uses thereof - Google Patents

Lithium-ion capacitor, manufacturing method for same, and uses thereof Download PDF

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WO2022088610A1
WO2022088610A1 PCT/CN2021/085412 CN2021085412W WO2022088610A1 WO 2022088610 A1 WO2022088610 A1 WO 2022088610A1 CN 2021085412 W CN2021085412 W CN 2021085412W WO 2022088610 A1 WO2022088610 A1 WO 2022088610A1
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negative electrode
positive electrode
carbon
lithium
ion capacitor
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PCT/CN2021/085412
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French (fr)
Chinese (zh)
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杨重阳
夏恒恒
徐雪茹
索路路
薛鑫
孙超
安仲勋
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上海奥威科技开发有限公司
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Publication of WO2022088610A1 publication Critical patent/WO2022088610A1/en

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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
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
    • H01G11/84—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

Definitions

  • the invention belongs to the field of energy storage, and relates to a lithium ion capacitor and a preparation method and application thereof.
  • Lithium-ion capacitors are an energy storage device between electric double-layer capacitors and lithium-ion batteries, combining the advantages of electric double-layer capacitors with high power density, long cycle life and high energy density of lithium-ion batteries.
  • Public transportation, marine transportation, electric locomotives, AGVs, heavy-duty equipment, energy storage and other fields have received extensive attention and applications.
  • Lithium iron phosphate has the characteristics of excellent safety performance, high temperature performance, environmental protection and no pollution, and is widely used in the cathode material of lithium ion batteries, but its low temperature performance is poor, the internal resistance is large and the lithium ion migration rate is low, resulting in poor rate performance, which directly limits phosphoric acid.
  • CN109994724A discloses a high specific energy lithium ion battery.
  • the positive electrode active material adopts composite porous carbon lithium iron phosphate or micro-nano-structured lithium iron phosphate coated with porous carbon layer after doped with metal, and the negative electrode active material adopts hard carbon material or
  • the lithium-ion battery prepared by coating nano-silicon or nano-silicon-coated conductive layer with hard carbon material has high specific energy, high rate charge and discharge, long cycle life and excellent low temperature performance.
  • the preparation of lithium-ion batteries only focuses on the combination and pairing of positive and negative materials, and the production process of the entire monomer, including the production process of positive and negative plates, separators, electrolytes, and current collectors, has not been optimized and improved.
  • CN102751496A discloses a preparation method for obtaining LiFePO 4 /graphene composite by preparing Fe 2 O 3 /graphene composite as a precursor, and then obtaining LiFePO 4 /graphene composite through solvothermal reaction.
  • the process is complicated and the electrochemical performance of the obtained composite material is unstable.
  • the cost of preparing graphene is too high.
  • the output of graphene in China is not high.
  • the performance of the composite electrode material prepared by using graphene has not been greatly improved, so it is difficult to industrialize the lithium iron phosphate/graphene composite electrode material. application.
  • CN101752561A discloses a graphene-modified lithium iron phosphate cathode composite material, a preparation method thereof, and a lithium ion secondary battery based on the cathode active material.
  • the method is to disperse graphene or graphene oxide and lithium iron phosphate in an aqueous solution , uniformly mixed by stirring and ultrasonic, followed by drying and annealing to obtain graphene-modified lithium iron phosphate cathode active material.
  • this method can modify lithium iron phosphate, it uses hydrogen as reducing gas and protective gas, which has low safety performance and uses organic electrolyte, which causes great environmental pollution.
  • the lithium iron phosphate cannot be effectively combined with graphene.
  • the lithium iron phosphate cannot be effectively combined with graphene.
  • the lithium iron phosphate cannot be effectively combined with graphene.
  • the purpose of the present invention is to provide a lithium ion capacitor and its preparation method and use.
  • the positive and negative active materials with suitable parameters are optimized, the material compounding and proportioning are optimized, the internal resistance of the current collector is reduced, the diaphragm with high porosity and low air permeability is preferred, and the electrical conductivity of the electrolyte at room temperature and low temperature is improved.
  • the compaction density and surface resistance are precisely controlled, the conductivity of the pole piece and the wettability of the electrolyte are improved, and the polarization is reduced, thereby improving the rate performance and low temperature performance of the lithium iron phosphate lithium ion capacitor.
  • the present invention provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, an electric double layer material, a conductive agent and a binder; The material of the negative electrode includes a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder.
  • the invention improves the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode by compounding materials with high conductivity, high rate and electric double layer properties, and improves the rate performance and low temperature performance of the positive electrode.
  • Carbon materials are used as negative electrode materials to improve the rate and low temperature performance of the negative electrode, thereby improving the rate performance and low temperature performance of lithium iron phosphate lithium-ion capacitors.
  • the reason why the interplanar spacing of the carbon material is at least 0.345 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery.
  • the interplanar spacing of the carbon material is at least 0.345 nm, for example, the interplanar spacing is greater than or equal to 0.345 nm or 0.352 nm, and the interplanar spacing is greater than or equal to 0.38 nm or 0.382 nm.
  • the mass ratio of the lithium iron phosphate, the electric double layer material, the conductive agent and the binder is (45-90):(5-45):(3-10):(2-10), for example 45 :45:5:5, 90:5:3:2, 86:5:3.5:5.5, 85:7:3:5, 70:20:4:6 or 80:10:5:5, etc.
  • the material of the positive electrode may include: 45-90% lithium iron phosphate, 5-45% electric double layer material, 3-10% conductive agent and 2-10% binder.
  • the mass percentage of the lithium iron phosphate can be, for example, 45%, 48%, 50%, 60%, 70%, 80% or 90%, etc.
  • the mass percentage of the electric double layer material can be, for example, 5%, 10%, 20%, 30%, 40% or 45%, etc.
  • the mass percentage of the conductive agent can be, for example, 3%, 5%, 8% or 10%, etc.
  • the mass percentage of the binder can be, for example, 2%, 5%, 8% or 10% etc.
  • the D50 of the lithium iron phosphate is 0.5-10 ⁇ m, for example, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, or 10 ⁇ m.
  • the reason why the median particle size of the lithium iron phosphate is in the micron level and in the range of 0.5-10 ⁇ m is that the particle size is too large, the magnification of lithium iron phosphate is low, and the particle size is too small, which has a negative impact on dispersion. There are many difficulties, and the side reactions of lithium-ion capacitors increase.
  • the specific surface area of the electric double layer material is 800-3600 m 2 /g, such as 800 m 2 /g, 1000 m 2 /g, 1500 m 2 /g, 2000 m 2 /g, 2500 m 2 /g, 3000 m 2 /g , 3500m 2 /g or 3600m 2 /g, etc.
  • the electric double layer material includes a porous carbon material.
  • the porous carbon material has obvious electric double layer characteristics, and cooperates with lithium iron phosphate to effectively improve the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode, and further improve the rate performance of the positive electrode and low temperature performance.
  • the mass ratio of the lithium iron phosphate to the porous carbon material is (1-18):1, such as 1:1, 5:1, 10:1, 5:1 or 18:1, etc.
  • the porous carbon material includes any one or a combination of at least two of activated carbon, carbon nanotubes, mesoporous carbon, carbon aerogel, framework carbon or graphene.
  • the conductive agent in the material of the positive electrode includes any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene.
  • the binder in the material of the positive electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
  • the mass ratio of the carbon material with the interplanar spacing d002 of at least 0.345 nm, the conductive agent and the binder is (80-98):(0.001-10):(2-10), for example 80:10: 10, 90:5:5, 91:2:7, 92:2.5:5.5, 90:6:4 or 93:2:5, etc.
  • the material of the negative electrode may include: 80-98% of the carbon material, 0.001-10%, and 2-10% of the binder.
  • the mass percentage of the carbon material may be, for example, 80%, 82%, 85%, 90%, 95%, or 98%, etc.
  • the mass percentage of the conductive agent may be, for example, 0.001%, 1%, 5%, 8% or 10%, etc.
  • the mass percentage of the binder can be, for example, 2%, 5%, 8% or 10%, etc.
  • the carbon material with the interplanar spacing d002 of at least 0.345 nm includes hard carbon and/or soft carbon.
  • the D50 of the hard carbon is 0.5-15 ⁇ m, such as 0.5 ⁇ m, 13 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m or 15 ⁇ m, and the like.
  • the interplanar spacing d002 of the hard carbon is greater than or equal to 0.38 nm, such as 0.38 nm, 0.4 nm, 0.42 nm, or 0.45 nm.
  • interplanar spacing d002 of the hard carbon is set to be greater than or equal to 0.38 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery.
  • the D50 of the soft carbon is 2-20 ⁇ m, such as 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m or 20 ⁇ m, and the like.
  • the interplanar spacing d002 of the soft carbon is greater than or equal to 0.345 nm, for example, 0.345 nm, 0.35 nm, 0.38 nm, or 0.4 nm.
  • interplanar spacing d002 of the selected soft carbon material is greater than or equal to 0.345 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery. .
  • the conductive agent in the material of the negative electrode includes any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene.
  • the binder in the material of the negative electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
  • the separator comprises any one or at least two of cellulose separator, PET non-woven separator, aramid separator, PET non-woven ceramic filled separator, PE ceramic coated separator or PP ceramic coated separator. combination.
  • the porosity of the membrane is greater than or equal to 45%, such as 45%, 46%, 47%, 48%, 49% or 50%, etc.
  • a porosity greater than or equal to 45% is conducive to high-rate charge and discharge of lithium-ion capacitors. If the porosity of the separator is less than 45%, the charge-discharge performance will decrease at high rates.
  • the air permeability of the membrane is less than or equal to 200s/100mL, such as 200s/100mL, 180s/100mL, 150s/100mL, 130s/100mL or 100s/100mL, etc.
  • the electrolyte includes lithium hexafluorophosphate, a solvent and additives.
  • the molar concentration of the lithium hexafluorophosphate is 0.8-1.5 mol/L, such as 0.8 mol/L, 0.9 mol/L, 1 mol/L, 1.1 mol/L, 1.2 mol/L, 1.3 mol/L, 1.4 mol/L L or 1.5mol/L, etc.
  • the solvent includes ethylene carbonate, ethyl methyl carbonate, ethyl acetate and ethyl propionate.
  • the mass fraction of the ethylene carbonate in the electrolyte is 7-13 wt %, for example, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt % or 13 wt %, etc.
  • the mass fraction of the ethyl methyl carbonate in the electrolyte is 7-13 wt %, for example, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt % or 13 wt %, etc.
  • the mass fraction of the ethyl acetate in the electrolyte is 70-80wt%, such as 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt% , 79wt% or 80wt%, etc.
  • the mass fraction of the ethyl propionate in the electrolyte is 1 to 5 wt %, for example, 1 wt %, 2 wt %, 3 wt %, 4 wt %, or 5 wt %.
  • the additives include vinylene carbonate, fluoroethylene carbonate and vinyl sulfate.
  • the mass fraction of the vinylene carbonate in the electrolyte is 1-2wt%, for example, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt% %, 1.7 wt %, 1.8 wt %, 1.9 wt % or 2 wt %, etc.
  • the mass fraction of the fluoroethylene carbonate in the electrolyte is 0.5 to 1.5 wt %, such as 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.1 wt %, 1.2 wt %, 1.3 wt %, 1.4 wt % or 1.5 wt %, etc.
  • the mass fraction of the vinyl sulfate in the electrolyte is 0.5-1.5wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt% %, 1.2 wt %, 1.3 wt %, 1.4 wt % or 1.5 wt %, etc.
  • the room temperature ionic conductivity of the electrolyte is greater than or equal to 12 mS/cm, 12 mS/cm, 13 mS/cm, 14 mS/cm, 15 mS/cm or 16 mS/cm, and the like.
  • the present invention provides a preparation method of a lithium ion capacitor as described in the first aspect, the preparation method comprising:
  • the preparation method of the positive electrode includes: mixing lithium iron phosphate, an electric double layer material, a conductive agent and a binder to prepare a slurry, coating the slurry on the positive electrode current collector, drying, and rolling to obtain the obtained slurry. the positive electrode;
  • the preparation method of the negative electrode includes: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder to prepare a slurry, coating the negative electrode current collector, drying, and rolling to obtain the negative electrode.
  • the present invention improves the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode by compounding materials with high conductivity and high rate with electric double layer characteristics, and improves the rate performance and low temperature performance of the positive electrode,
  • a carbon material with a large interplanar spacing d002 is selected to prepare the negative electrode material to improve the rate and low temperature performance of the negative electrode, thereby improving the rate performance and low temperature performance of the lithium iron phosphate lithium ion capacitor.
  • the positive electrode and the negative electrode are respectively cut to obtain a positive electrode sheet and a negative electrode sheet, which are then stacked with the separator.
  • the apparatus for the stacking operation is an automatic stacker.
  • one metal lithium sheet is placed on each side of the superimposed battery cell.
  • high temperature drying, ultrasonic welding and top and side sealing operations are performed on the superposed cells before the operation of injecting the electrolyte.
  • the compacted density of the rolled positive electrode is 1.3-2.2 g/cm 3 , for example, 1.3 g/cm 3 , 1.5 g/cm 3 , 1.8 g/cm 3 , 2 g/cm 3 , 2.1 g/cm 3 . cm 3 or 2.2g/cm 3 etc.
  • Controlling the compaction density of cathode materials in the range of 1.3 to 2.2 g/ cm3 is crucial for rate performance and low temperature performance.
  • the thickness of the positive electrode current collector is 15-30 ⁇ m, for example, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 23 ⁇ m, 25 ⁇ m, 28 ⁇ m, or 30 ⁇ m.
  • the positive electrode current collector comprises any one or a combination of at least two of aluminum foil, aluminum mesh or surface-treated aluminum foil coated with conductive coating on the surface.
  • the positive surface resistance of the positive electrode is less than or equal to 10 ⁇ cm 2 , such as 10 ⁇ cm 2 , 9 ⁇ cm 2 , 8 ⁇ cm 2 , 7 ⁇ cm 2 , 6 ⁇ cm 2 or 5 ⁇ cm 2 , etc.
  • Controlling the positive surface resistance of the positive electrode within the above-mentioned range is crucial for the rate performance of the lithium ion capacitor.
  • the compaction density of the negative electrode after rolling is 0.8-1.4 g/cm 3 , for example, 0.8 g/cm 3 , 0.9 g/cm 3 , 1 g/cm 3 , 1.1 g/cm 3 , 1.2 g/cm 3 . cm 3 , 1.3g/cm 3 or 1.4g/cm 3 etc.
  • Controlling the compaction density of anode materials is critical for rate capability and low temperature performance.
  • the thickness of the negative electrode current collector is 10-25 ⁇ m, for example, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 23 ⁇ m, or 25 ⁇ m.
  • the negative electrode current collector comprises any one or a combination of at least two of copper foil, copper mesh or surface-treated copper foil coated with a conductive coating on the surface.
  • the negative surface resistance of the negative electrode is less than or equal to 3 ⁇ cm 2 , such as 3 ⁇ cm 2 , 2.5 ⁇ cm 2 , 2 ⁇ cm 2 or 1.5 ⁇ cm 2 , and the like.
  • Controlling the negative surface resistance of the negative electrode within the above-mentioned range is crucial for the rate performance of the lithium ion capacitor.
  • the ratio N/P ratio of the specific capacity of the negative electrode and the specific capacity of the positive electrode is 2 ⁇ 3.5, such as 2, 2.2, 2.5, 2.8, 3, 3.3 or 3.5, etc.
  • the preparation method of the lithium ion capacitor includes:
  • the preparation method of the positive electrode comprises: mixing lithium iron phosphate, porous carbon, conductive agent and binder according to the mass ratio of (45-90):(5-45):(3-10):(2-10) Slurry is made, coated on a positive electrode current collector with a thickness of 15-30 ⁇ m, dried, rolled, and compacted at a density of 1.3-2.2 g/cm 3 to obtain the positive electrode whose positive surface resistance of the positive electrode is less than or is equal to 10 ⁇ cm 2 ;
  • the preparation method of the negative electrode includes: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder in a mass ratio of (80-98):(0-10):(2-10) Slurry is formed, coated on a negative electrode current collector with a thickness of 10-25 ⁇ m, dried, and rolled to obtain the negative electrode, and the negative electrode surface resistance of the negative electrode is less than or equal to 3 ⁇ cm 2 .
  • the present invention also provides a use of the lithium ion capacitor according to the first aspect, the use comprising using the lithium ion capacitor as an energy storage device.
  • the present invention has the following beneficial effects:
  • the positive and negative active materials with suitable parameters are optimized, the material compounding and proportioning are optimized, the internal resistance of the current collector is reduced, the diaphragm with high porosity and low air permeability is preferred, and the electrical conductivity of the electrolyte at room temperature and low temperature is improved.
  • the compaction density and surface resistance are precisely controlled, which improves the conductivity of the pole piece and the wettability of the electrolyte, and reduces the polarization, thereby improving the rate performance and low temperature performance of lithium iron phosphate lithium ion capacitors.
  • the chemical power source prepared by the present invention has high rate (5C capacity is more than 96% of 1C) and excellent low temperature performance (-20°C is more than 79% of 25°C), and also With the characteristics of high safety and low cost, it provides guarantee for applications in the marine and military fields, and is conducive to expanding the market share of lithium-ion capacitors.
  • FIG. 1 shows the discharge curves of the lithium ion capacitor provided in Example 1 at 1C and 5C.
  • Example 2 is a 5C discharge curve of the lithium ion capacitor provided in Example 2 at 25°C and -20°C.
  • This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a PET non-woven separator and an electrolyte;
  • the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and conductive graphite as conductive agents , using polyvinylidene fluoride as a binder;
  • the material of the negative electrode includes a hard carbon material with a crystal plane spacing d002 of 0.382nm, carbon black and carbon nanotubes as a conductive agent, and polyvinylidene fluoride as a binder;
  • the room temperature ionic conductivity of the electrolyte solution is 14mS/cm
  • the electrolyte solution includes 1.1mol/L lithium hexafluorophosphate, 8wt% ethylene carbonate, 10wt% ethyl methyl carbonate, 76wt% ethyl acetate and 3 wt % of ethyl propionate, 1 wt % of vinylene carbonate, 1 wt % of fluoroethylene carbonate and 1 wt % of vinyl sulfate.
  • the above weight fractions are based on the total mass of additives and solvents as 100%).
  • the preparation method of the lithium ion capacitor is as follows:
  • Preparation of positive electrode use lithium iron phosphate with D50 of 6 ⁇ m and activated carbon with specific surface area of 1600 m 2 /g as electric double layer material, carbon black, conductive graphite and polyvinylidene fluoride according to the mass ratio of 86:5:3.5:1.5: 4.
  • slurry uniformly coated on carbon-coated aluminum foil with a thickness of 20 ⁇ m, dried, rolled, and compacted at a density of 2.05 g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled not to exceed 3 ⁇ cm 2 .
  • Negative electrode preparation Mix hard carbon material with D50 of 5 ⁇ m and d002 of 0.382nm, carbon black, carbon nanotubes and polyvinylidene fluoride in a mass ratio of 91:1.5:0.5:7 to make a slurry, which is uniformly coated on the The carbon-coated copper foil with a thickness of 12 ⁇ m was dried, rolled, and the compacted density was 1.0 g /cm 3 to obtain a negative electrode material.
  • the diaphragm is a PET non-woven diaphragm with a porosity of 54% and an air permeability of 11s/100mL;
  • the electrolyte consists of 1.1mol/L lithium hexafluorophosphate, 8wt% ethylene carbonate, 10wt% methyl ethyl carbonate, 75wt% ethyl acetate and 3wt% ethyl propionate, 1wt% vinylene carbonate, It is composed of 1wt% of fluoroethylene carbonate and 1wt% of ethylene sulfate, (the above weight fraction is based on the electrolyte as 100%) and the room temperature ionic conductivity is 14mS/cm;
  • Preparation of lithium ion capacitors The positive and negative pole pieces are cut into pole pieces, and the PET non-woven fabric separator is stacked on an automatic laminating machine in a Z shape to form a battery cell, and a metal lithium piece is placed on each side of the battery core. High temperature drying, ultrasonic welding, top and side sealing, electrolyte injection, air extraction, sealing and other steps to obtain the final flexible packaging lithium ion capacitor using lithium iron phosphate.
  • This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a cellulose separator and an electrolyte;
  • the material of the positive electrode includes lithium iron phosphate, mesoporous carbon, carbon black and vapor-grown carbon fiber as conductive materials using polyvinylidene fluoride as a binder;
  • the material of the negative electrode includes a soft carbon material with a crystal plane spacing d002 of 0.352nm, carbon black and graphene as a conductive agent, and polyacrylate as a binder;
  • the room temperature ionic conductivity of the electrolyte solution is 12.5mS/cm
  • the electrolyte solution includes 1.05mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 10wt% ethyl methyl carbonate, 75wt% ethyl acetate ester and 3 wt % ethyl propionate, 1 wt % vinylene carbonate, 0.5 wt % fluoroethylene carbonate and 0.5 wt % vinyl sulfate.
  • the above weight fractions are based on the total mass of additives and solvents as 100%).
  • the preparation method of the lithium ion capacitor is as follows:
  • a. Preparation of positive electrode Lithium iron phosphate with D50 of 7 ⁇ m, mesoporous carbon with specific surface area of 1800 m 2 /g as electric double layer material, carbon black, vapor-grown carbon fiber and polyvinylidene fluoride in a mass ratio of 85:7:3 :1:4 mixed into slurry, uniformly coated on 21 ⁇ m-thick corroded aluminum foil, dried, rolled, and compacted at a density of 2g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled not to exceed 2.5 ⁇ cm 2 .
  • Negative electrode preparation Mix soft carbon, carbon black, graphene and polyacrylate with a D50 of 6 ⁇ m and a d002 of 0.352 nm according to the mass ratio of 92:2:0.5:5.5 to make a slurry, which is uniformly coated on a thickness of 12 ⁇ m
  • the carbon-coated copper foil was dried, rolled, and the compacted density was 1.3 g /cm 3 to obtain a negative electrode material.
  • the diaphragm is a cellulose diaphragm with a porosity of 70% and an air permeability of 7s/100mL;
  • the electrolyte consists of 1.05mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 10wt% methyl ethyl carbonate, 75wt% ethyl acetate and 3wt% ethyl propionate, 1wt% vinylene carbonate, It is composed of 0.5wt% of fluoroethylene carbonate and 0.5wt% of ethylene sulfate, (the above weight fraction is based on the electrolyte solution as 100%) and the room temperature ionic conductivity is 12.5mS/cm;
  • Preparation of lithium ion capacitors Cut the positive and negative electrodes into pole pieces, and stack them with the cellulose separator in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
  • This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a PP ceramic separator and an electrolyte;
  • the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and conductive graphite as conductive agents, and Polyvinylidene fluoride is used as a binder;
  • the material of the negative electrode includes a hard carbon material with a crystal plane spacing d002 of 0.38 nm, carbon black and carbon nanotubes as conductive agents, sodium carboxymethyl cellulose and styrene-butadiene rubber as binder;
  • the room temperature ionic conductivity of the electrolyte solution is 14mS/cm
  • the electrolyte solution includes 1mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 7wt% ethyl methyl carbonate, 78wt% ethyl acetate and 2 wt% ethyl propionate, 1.5 wt% vinylene carbonate, 1 wt% fluoroethylene carbonate and 0.5 wt% vinyl sulfate. (The above weight fractions are based on the total mass of additives and solvents as 100%).
  • the preparation method of the lithium ion capacitor is as follows:
  • Positive electrode preparation The D50 of 3 ⁇ m lithium iron phosphate, the activated carbon with a specific surface area of 2240m 2/ g is used as the electric double layer material, carbon black, conductive graphite and polyvinylidene fluoride according to the mass ratio of 70:20:4:1: 5. Mixed to make a slurry, uniformly coated on 22 ⁇ m thick corroded aluminum foil, dried, rolled, and compacted to a density of 1.8g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled to be no more than 3.5 ⁇ cm 2 .
  • the diaphragm is a PP ceramic diaphragm, with a porosity of 50% and an air permeability of 187s/100mL;
  • the electrolyte consists of 1mol lithium hexafluorophosphate, 10wt% ethylene carbonate, 7wt% methyl ethyl carbonate, 78wt% ethyl acetate and 2wt% ethyl propionate, 1.5wt% vinylene carbonate, 1wt% fluoroethylene carbonate It is composed of 0.5wt% vinyl sulfate, (the above mass fraction is based on the electrolyte as 100%), and the room temperature ionic conductivity is 14mS/cm;
  • Preparation of lithium ion capacitors Cut the positive and negative electrodes into pole pieces, and stack them with the PP ceramic diaphragm in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the battery cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
  • This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a cellulose separator and an electrolyte;
  • the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and vapor-grown carbon fiber as conductive agents, Using polyacrylic acid as a binder;
  • the material of the negative electrode includes a soft carbon material with a crystal plane spacing d002 of 0.35 nm, carbon black and vapor-grown carbon fiber as a conductive agent, and polyvinylidene fluoride as a binder;
  • the room temperature ionic conductivity of the electrolyte solution is 12mS/cm
  • the electrolyte solution includes 1.2mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 13wt% ethyl methyl carbonate, 70wt% ethyl acetate and 3.5 wt% ethyl propionate, 1.5 wt% vinylene carbonate, 1 wt% fluoroethylene carbonate and 1 wt% vinyl sulfate. ((The above weight fraction is based on the total mass of additives and solvents as 100%).
  • the preparation method of the lithium ion capacitor is as follows:
  • Lithium iron phosphate with D50 of 1.5 ⁇ m and activated carbon with specific surface area of 1800 m 2 /g are used as electric double layer material, carbon black, vapor grown carbon fiber and polyacrylic acid according to the mass ratio of 80:10:2.5:2.5: 5.
  • Negative electrode preparation Mix soft carbon material with D50 of 8 ⁇ m and d002 of 0.35 nm, carbon black, carbon nanotubes and polyvinylidene fluoride in a mass ratio of 93:1:1:5 to make a slurry, which is uniformly coated on the The carbon-coated copper foil with a thickness of 12 ⁇ m was dried, rolled, and the compacted density was 1.25 g /cm 3 to obtain a negative electrode material.
  • the diaphragm is an aramid diaphragm, with a porosity of 54% and an air permeability of 5s/100mL;
  • the electrolyte consists of 1.2mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 13wt% methyl ethyl carbonate, 70wt% ethyl acetate and 3.5wt% ethyl propionate, 1.5wt% vinylene carbonate, 1wt% fluorine It is composed of ethylene carbonate and 1wt% ethylene sulfate, (the above weight fraction is based on the electrolyte as 100%), and the ionic conductivity at room temperature is 12mS/cm;
  • Preparation of lithium ion capacitors Cut the positive and negative electrodes into pole pieces, and stack them with the aramid membrane in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the battery cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is: in the preparation process of the positive electrode in this embodiment, lithium iron phosphate with D50 of 6 ⁇ m and activated carbon with a specific surface area of 1600 m 2 /g are used as electric double layer material, carbon black, conductive graphite and polymer Vinylidene fluoride was adjusted to a mass ratio of 91:4:2.5:1.5:1 and mixed to make a slurry.
  • Example 1 The difference between this example and Example 1 is: in the process of preparing the negative electrode material in this example, the hard carbon, carbon black, carbon nanotube and polyvinylidene fluoride with D50 of 5 ⁇ m and d002 of 0.382 nm were adjusted to 98.5 by mass ratio. :0.3:0.2:1 mixed to make slurry.
  • the positive electrode surface resistance of the positive electrode in this embodiment is 6 ⁇ cm 2 .
  • the negative electrode sheet resistance of the negative electrode in this embodiment is 4 ⁇ cm 2 .
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the D50 of the lithium iron phosphate in the positive electrode material of this embodiment is 20 ⁇ m.
  • Example 1 The difference between this example and Example 1 is that the interplanar spacing d002 of the hard carbon material in the negative electrode material of this comparative example is 0.37 nm.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, in the process of preparing the positive electrode, no activated carbon material is added, but only an active material such as lithium iron phosphate.
  • Test standard QCT741-2014 standard for automotive supercapacitors.
  • Table 1 shows the electrochemical properties of the lithium ion capacitors prepared in Examples 1-10 and Comparative Example 1.
  • the lithium ion capacitor provided by the present invention has high rate (5C capacity is more than 96% of 1C) and excellent low temperature performance (-20°C is more than 79% of 25°C).
  • Example 1 From the data results of Example 1 and Examples 5 and 6, it can be seen that in the process of preparing the positive electrode material or the negative electrode material, the mass ratio of the raw materials used exceeds the preferred mass ratio of the present invention, and the rate and low temperature performance will be reduced. The reason is that the conductivity and adhesiveness of the electrodes are deteriorated.
  • Example 1 From the data results of Example 1 and Examples 7 and 8, it can be seen that whether the positive surface resistance is higher or the negative surface resistance is higher, it will affect the rate performance and low temperature performance of the lithium ion capacitor, and its performance will be reduced.
  • Example 10 From the data results of Example 1 and Example 10, it can be seen that if the interplanar spacing d002 of the carbon material in the negative electrode material is too small, the lithium ion intercalation and extraction ability of the negative electrode will be deteriorated, thereby affecting the rate performance and low temperature performance.
  • Example 1 It can be seen from the data results of Example 1 and Comparative Example 1 that only lithium iron phosphate is used as the positive electrode active material, and the rate performance is deteriorated when no electric double layer material is added.

Abstract

Provided are a lithium-ion capacitor, a manufacturing method for same, and uses thereof. The lithium-ion capacitor comprises a positive electrode, a negative electrode, a separator, and an electrolytic solution. The materials of the positive electrode comprise lithium iron phosphate, an electrical double-layered material, an electrically-conductive agent, and an adhesive agent. The materials of the negative electrode comprise a carbon material of which the interplanar spacing d002 is at least 0.345 nm, an electrically-conductive agent, and an adhesive agent. By means of preferred positive and negative electrode active substances having suitable parameters, the compounding and proportioning of the materials are optimized, the internal resistance of a current collector is reduced, the separator having high porosity and low air permeability is preferred, the electrical conductivity of the electrolytic solution in room temperature and low temperatures is increased, compaction density and sheet resistance are precisely controlled, the electrical conductivity of electrode tabs and the wettability of the electrolytic solution are increased, and polarization is reduced, thus increasing the rate performance and low-temperature performance of the lithium-ion capacitor using lithium iron phosphate.

Description

一种锂离子电容器及其制备方法和用途A kind of lithium ion capacitor and its preparation method and use 技术领域technical field
本发明属于储能领域，涉及一种锂离子电容器及其制备方法和用途。The invention belongs to the field of energy storage, and relates to a lithium ion capacitor and a preparation method and application thereof.
背景技术Background technique
锂离子电容器是一种介于双电层电容器和锂离子电池之间的储能器件，结合了双电层电容器高功率密度、长循环寿命和锂离子电池高能量密度的优点，在轨道交通，公共交通、船舶交通、电机车、AGV、重载设备、储能等领域得到广泛的关注和应用。Lithium-ion capacitors are an energy storage device between electric double-layer capacitors and lithium-ion batteries, combining the advantages of electric double-layer capacitors with high power density, long cycle life and high energy density of lithium-ion batteries. Public transportation, marine transportation, electric locomotives, AGVs, heavy-duty equipment, energy storage and other fields have received extensive attention and applications.
磷酸铁锂具有优异的安全性能、高温性能、环保无污染的特点，广泛用于锂离子电池正极材料，但其低温性能差，内阻大和锂离子迁移速率低造成倍率性能差，直接限制了磷酸铁锂在锂离子电容器中的推广应用。Lithium iron phosphate has the characteristics of excellent safety performance, high temperature performance, environmental protection and no pollution, and is widely used in the cathode material of lithium ion batteries, but its low temperature performance is poor, the internal resistance is large and the lithium ion migration rate is low, resulting in poor rate performance, which directly limits phosphoric acid. The promotion and application of iron-lithium in lithium-ion capacitors.
CN109994724A中公开了一种高比能量锂离子电池，正极活性物质采用复合多孔炭的磷酸铁锂或掺杂金属后裹覆多孔炭层的微纳结构磷酸铁锂，负极活性物质采用硬碳材料或由硬碳材料包覆纳米硅或纳米硅裹覆导电层后与硬碳材料复合，制备的锂离子电池具有高比能量、高倍率充放电、长循环寿命和优越的低温性能。但锂离子电池的制备仅着眼于正负极材料的组合配对，未对整个单体的制作工艺包括正负极片的制作工艺、隔膜、电解液、集流体等进行优化改善。CN109994724A discloses a high specific energy lithium ion battery. The positive electrode active material adopts composite porous carbon lithium iron phosphate or micro-nano-structured lithium iron phosphate coated with porous carbon layer after doped with metal, and the negative electrode active material adopts hard carbon material or The lithium-ion battery prepared by coating nano-silicon or nano-silicon-coated conductive layer with hard carbon material has high specific energy, high rate charge and discharge, long cycle life and excellent low temperature performance. However, the preparation of lithium-ion batteries only focuses on the combination and pairing of positive and negative materials, and the production process of the entire monomer, including the production process of positive and negative plates, separators, electrolytes, and current collectors, has not been optimized and improved.
CN102751496A公开了一种通过制备Fe 2O 3/石墨烯复合物作为前驱体，然后通过溶剂热反应得到LiFePO 4/石墨烯复合物的制备方法，然而其过程比较繁琐，所得复合材料的电化学性能不稳定。同时现在制备石墨烯成本过高，同时中国石墨烯产量不高，使用石墨烯制备得到的复合电极材料性能并没有特别大的提升，所以使磷酸铁锂/石墨烯复合电极材料很难进行产业化应用。 CN102751496A discloses a preparation method for obtaining LiFePO 4 /graphene composite by preparing Fe 2 O 3 /graphene composite as a precursor, and then obtaining LiFePO 4 /graphene composite through solvothermal reaction. However, the process is complicated and the electrochemical performance of the obtained composite material is unstable. At the same time, the cost of preparing graphene is too high. At the same time, the output of graphene in China is not high. The performance of the composite electrode material prepared by using graphene has not been greatly improved, so it is difficult to industrialize the lithium iron phosphate/graphene composite electrode material. application.
CN101752561A公开了一种石墨烯改性磷酸铁锂正极复合材料及其制备方法和基于该正极活性材料的锂离子二次电池，该方法是将石墨烯或者氧化石墨烯与磷酸铁锂分散于水溶液中，通过搅拌和超声使其均匀混合，随后通过干燥和退火得到石墨烯改性的磷酸铁锂正极活性材料。这种方法虽然可以改性磷酸铁锂，但是其使用氢气作为还原气体和保护气体，安全性能低，使用有机电解液，环境污染大。并且由于是将预先制备的磷酸铁锂与石墨烯或者氧化石墨烯通过简单的机械方法混合，获得石墨烯共混改性的磷酸铁锂正极活性材料，磷酸铁锂不能有效地与石墨烯复合而充分地利用石墨烯优异的电化学性能。此外由于石墨的层间距较小，不能够有效地与其他物质***复合，CN101752561A discloses a graphene-modified lithium iron phosphate cathode composite material, a preparation method thereof, and a lithium ion secondary battery based on the cathode active material. The method is to disperse graphene or graphene oxide and lithium iron phosphate in an aqueous solution , uniformly mixed by stirring and ultrasonic, followed by drying and annealing to obtain graphene-modified lithium iron phosphate cathode active material. Although this method can modify lithium iron phosphate, it uses hydrogen as reducing gas and protective gas, which has low safety performance and uses organic electrolyte, which causes great environmental pollution. And because the pre-prepared lithium iron phosphate is mixed with graphene or graphene oxide by a simple mechanical method to obtain a graphene blend-modified lithium iron phosphate cathode active material, the lithium iron phosphate cannot be effectively combined with graphene. Take full advantage of the excellent electrochemical properties of graphene. In addition, due to the small interlayer spacing of graphite, it cannot effectively intercalate with other substances.
如何解决磷酸铁锂应用于锂离子电容器时出现的低温性能差，内阻大和锂离子迁移速率低造成倍率性能差等问题，是值得考虑的。It is worth considering how to solve the problems of poor low temperature performance, poor rate performance caused by large internal resistance and low lithium ion migration rate when lithium iron phosphate is applied to lithium ion capacitors.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种锂离子电容器及其制备方法和用途。本发明通过优选合适参数的正负极活性物质，优化材料复配和配比，降低集流体内阻，优选高孔隙率低透气度的隔膜，提高电解液在常温和低温下的电导率，对压实密度和面电阻进行精确控制，提高 极片的导电能力和电解液的浸润性，减小极化，从而提高了使用磷酸铁锂锂离子电容器的倍率性能和低温性能。The purpose of the present invention is to provide a lithium ion capacitor and its preparation method and use. In the present invention, the positive and negative active materials with suitable parameters are optimized, the material compounding and proportioning are optimized, the internal resistance of the current collector is reduced, the diaphragm with high porosity and low air permeability is preferred, and the electrical conductivity of the electrolyte at room temperature and low temperature is improved. The compaction density and surface resistance are precisely controlled, the conductivity of the pole piece and the wettability of the electrolyte are improved, and the polarization is reduced, thereby improving the rate performance and low temperature performance of the lithium iron phosphate lithium ion capacitor.
为达到此发明目的，本发明采用以下技术方案：In order to achieve this object of the invention, the present invention adopts the following technical solutions:
第一方面，本发明提供一种锂离子电容器，所述锂离子电容器包括正极、负极、隔膜和电解液；所述正极的材料包括磷酸铁锂、双电层材料、导电剂和粘结剂；所述负极的材料包括晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂。In a first aspect, the present invention provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, an electric double layer material, a conductive agent and a binder; The material of the negative electrode includes a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder.
本发明通过复配高电导率高倍率具有双电层特性的材料来改善磷酸铁锂正极锂离子迁移速率低的问题，提高了正极的倍率性能和低温性能，选用了晶面间距d002较大的碳材料作为负极材料来提高负极的倍率和低温性能，从而提高了使用磷酸铁锂锂离子电容器的倍率性能和低温性能。The invention improves the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode by compounding materials with high conductivity, high rate and electric double layer properties, and improves the rate performance and low temperature performance of the positive electrode. Carbon materials are used as negative electrode materials to improve the rate and low temperature performance of the negative electrode, thereby improving the rate performance and low temperature performance of lithium iron phosphate lithium-ion capacitors.
本发明中，所述碳材料的晶面间距至少为0.345nm的原因为，当晶面间距提高，负极的锂离子扩散速率会增大，能改善电池的倍率性能和低温性能。In the present invention, the reason why the interplanar spacing of the carbon material is at least 0.345 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery.
本发明中，所述碳材料的晶面间距至少为0.345nm，例如晶面间距大于等于0.345nm或0.352nm等，晶面间距大于等于0.38nm或者0.382nm等。In the present invention, the interplanar spacing of the carbon material is at least 0.345 nm, for example, the interplanar spacing is greater than or equal to 0.345 nm or 0.352 nm, and the interplanar spacing is greater than or equal to 0.38 nm or 0.382 nm.
优选地，所述磷酸铁锂、双电层材料、导电剂和粘结剂的质量比为(45～90):(5～45):(3～10):(2～10)，例如45:45:5:5、90:5:3:2、86:5:3.5:5.5、85:7:3:5、70:20:4:6或80:10:5:5等。Preferably, the mass ratio of the lithium iron phosphate, the electric double layer material, the conductive agent and the binder is (45-90):(5-45):(3-10):(2-10), for example 45 :45:5:5, 90:5:3:2, 86:5:3.5:5.5, 85:7:3:5, 70:20:4:6 or 80:10:5:5, etc.
示例性的，在所述正极的材料中，按照质量百分比可以包括：45～90％的磷酸铁锂、5～45％的双电层材料、3～10％的导电剂和2～10％的粘结剂。Exemplarily, in the material of the positive electrode, according to mass percentage, it may include: 45-90% lithium iron phosphate, 5-45% electric double layer material, 3-10% conductive agent and 2-10% binder.
具体的，所述磷酸铁锂的质量百分比例如可以是45％、48％、50％60％、70％、80％或90％等；所述双电层材料的质量百分比例如可以是5％、10％、20％、30％、40％或45％等；所述导电剂的质量百分比例如可以是3％、5％、8％或10％等；所述粘结剂的质量百分比例如可以是2％、5％、8％或10％等。Specifically, the mass percentage of the lithium iron phosphate can be, for example, 45%, 48%, 50%, 60%, 70%, 80% or 90%, etc.; the mass percentage of the electric double layer material can be, for example, 5%, 10%, 20%, 30%, 40% or 45%, etc.; the mass percentage of the conductive agent can be, for example, 3%, 5%, 8% or 10%, etc.; the mass percentage of the binder can be, for example, 2%, 5%, 8% or 10% etc.
所述磷酸铁锂、双电层材料、导电剂和粘结剂的质量比为(45～90):(5～45):(3～10):(2～10)的原因为尽管双电层材料增加能提高倍率性能，但太大的比例会降低正极活性物质的克容量，使锂离子电容器的能量密度降低。The reason why the mass ratio of the lithium iron phosphate, the electric double layer material, the conductive agent and the binder is (45～90):(5～45):(3～10):(2～10) is that although the double electric Increasing the layer material can improve the rate performance, but too large a ratio will reduce the gram capacity of the positive active material and reduce the energy density of the lithium-ion capacitor.
优选地，所述磷酸铁锂的D50为0.5～10μm，例如0.5μm、1μm、2μm、5μm、8μm或10μm等。Preferably, the D50 of the lithium iron phosphate is 0.5-10 μm, for example, 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, or 10 μm.
本发明中，所述磷酸铁锂的中值粒径为微米级别且在0.5～10μm范围内的原因为粒径太大，磷酸铁锂的倍率偏低，而粒径太小，对分散带来很多困难，并且锂离子电容器的副反应增多。In the present invention, the reason why the median particle size of the lithium iron phosphate is in the micron level and in the range of 0.5-10 μm is that the particle size is too large, the magnification of lithium iron phosphate is low, and the particle size is too small, which has a negative impact on dispersion. There are many difficulties, and the side reactions of lithium-ion capacitors increase.
优选地，所述双电层材料的比表面积为800～3600m 2/g，例如800m 2/g、1000m 2/g、1500m 2/g、2000m 2/g、2500m 2/g、3000m 2/g、3500m 2/g或3600m 2/g等。 Preferably, the specific surface area of the electric double layer material is 800-3600 m 2 /g, such as 800 m 2 /g, 1000 m 2 /g, 1500 m 2 /g, 2000 m 2 /g, 2500 m 2 /g, 3000 m 2 /g , 3500m 2 /g or 3600m 2 /g, etc.
优选地，所述双电层材料包括多孔碳材料。Preferably, the electric double layer material includes a porous carbon material.
本发明中，多孔碳材料作为双电层材料，具有明显的双电层特性，与磷酸铁锂配合，有效地改善了磷酸铁锂正极锂离子迁移速率低的问题，进一步提高了正极的倍率性能和低温性能。In the present invention, as an electric double layer material, the porous carbon material has obvious electric double layer characteristics, and cooperates with lithium iron phosphate to effectively improve the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode, and further improve the rate performance of the positive electrode and low temperature performance.
优选地，所述磷酸铁锂和多孔碳材料的质量比为(1～18):1，例如1:1、5:1、10:1、5:1或18:1等。Preferably, the mass ratio of the lithium iron phosphate to the porous carbon material is (1-18):1, such as 1:1, 5:1, 10:1, 5:1 or 18:1, etc.
优选的，所述多孔碳材料包括活性炭、碳纳米管、介孔碳、碳气凝胶、骨架炭或石墨烯中的任意一种或至少两种的组合。Preferably, the porous carbon material includes any one or a combination of at least two of activated carbon, carbon nanotubes, mesoporous carbon, carbon aerogel, framework carbon or graphene.
优选地，所述正极的材料中的导电剂包括炭黑、导电石墨、气相生长碳纤维、碳纳米管或石墨烯中的任意一种或至少两种的组合。Preferably, the conductive agent in the material of the positive electrode includes any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene.
优选地，所述正极的材料中的粘结剂包括聚偏氟乙烯、羧甲基纤维素钠、丁苯橡胶、聚丙烯酸、聚四氟乙烯、聚丙烯腈或聚丙烯酸酯中的任意一种或至少两种的组合。Preferably, the binder in the material of the positive electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
优选地，所述晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂的质量比为(80～98):(0.001～10):(2～10)，例如80:10:10、90:5:5、91:2:7、92:2.5:5.5、90:6:4或93:2:5等。Preferably, the mass ratio of the carbon material with the interplanar spacing d002 of at least 0.345 nm, the conductive agent and the binder is (80-98):(0.001-10):(2-10), for example 80:10: 10, 90:5:5, 91:2:7, 92:2.5:5.5, 90:6:4 or 93:2:5, etc.
示例性的，在所述负极的材料中，按照质量百分比可以包括：80～98％的所述碳材料、0.001～10％、2～10％的粘结剂。Exemplarily, in the material of the negative electrode, according to mass percentage, it may include: 80-98% of the carbon material, 0.001-10%, and 2-10% of the binder.
具体的，所述碳材料的质量百分比例如可以是80％、82％、85％90％、95％或98％等；所述导电剂的质量百分比例如可以是0.001％、1％、5％、8％或10％等；所述粘结剂的质量百分比例如可以是2％、5％、8％或10％等。Specifically, the mass percentage of the carbon material may be, for example, 80%, 82%, 85%, 90%, 95%, or 98%, etc.; the mass percentage of the conductive agent may be, for example, 0.001%, 1%, 5%, 8% or 10%, etc.; the mass percentage of the binder can be, for example, 2%, 5%, 8% or 10%, etc.
优选地，所述晶面间距d002至少为0.345nm的碳材料包括硬碳和/或软碳。Preferably, the carbon material with the interplanar spacing d002 of at least 0.345 nm includes hard carbon and/or soft carbon.
优选地，所述硬碳的D50为0.5～15μm，例如0.5μm、13μm、5μm、8μm、10μm、12μm或15μm等。Preferably, the D50 of the hard carbon is 0.5-15 μm, such as 0.5 μm, 13 μm, 5 μm, 8 μm, 10 μm, 12 μm or 15 μm, and the like.
优选地，所述硬碳的晶面间距d002大于或等于0.38nm，例如0.38nm、、0.4nm、0.42nm或0.45nm等。Preferably, the interplanar spacing d002 of the hard carbon is greater than or equal to 0.38 nm, such as 0.38 nm, 0.4 nm, 0.42 nm, or 0.45 nm.
设置硬碳的晶面间距d002大于或等于0.38nm的原因为，当晶面间距提高，负极的锂离子扩散速率会增大，能改善电池的倍率性能和低温性能。The reason why the interplanar spacing d002 of the hard carbon is set to be greater than or equal to 0.38 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery.
优选地，所述软碳的D50为2～20μm，例如2μm、5μm、8μm、10μm、12μm、15μm、18μm或20μm等。Preferably, the D50 of the soft carbon is 2-20 μm, such as 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm, and the like.
优选地，所述软碳的晶面间距d002大于或等于0.345nm，例如0.345nm、0.35nm、0.38nm或0.4nm等。Preferably, the interplanar spacing d002 of the soft carbon is greater than or equal to 0.345 nm, for example, 0.345 nm, 0.35 nm, 0.38 nm, or 0.4 nm.
选用的软碳材料的晶面间距d002大于或等于0.345nm的原因为，当晶面间距提高时，负极的锂离子扩散速率会增大，能改善电池的倍率性能和低温性能。。The reason why the interplanar spacing d002 of the selected soft carbon material is greater than or equal to 0.345 nm is that when the interplanar spacing increases, the lithium ion diffusion rate of the negative electrode will increase, which can improve the rate performance and low temperature performance of the battery. .
优选地，所述负极的材料中的导电剂包括炭黑、导电石墨、气相生长碳纤维、碳纳米管或石墨烯中的任意一种或至少两种的组合。Preferably, the conductive agent in the material of the negative electrode includes any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene.
优选地，所述负极的材料中的粘结剂包括聚偏氟乙烯、羧甲基纤维素钠、丁苯橡胶、聚丙烯酸、聚四氟乙烯、聚丙烯腈或聚丙烯酸酯中的任意一种或至少两种的组合。Preferably, the binder in the material of the negative electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
优选地，所述隔膜包括纤维素隔膜、PET无纺布隔膜、芳纶隔膜、PET无纺布陶瓷填充隔膜、PE陶瓷涂覆隔膜或PP陶瓷涂覆隔膜中的任意一种或至少两种的组合。Preferably, the separator comprises any one or at least two of cellulose separator, PET non-woven separator, aramid separator, PET non-woven ceramic filled separator, PE ceramic coated separator or PP ceramic coated separator. combination.
优选地，所述隔膜的孔隙率大于或等于45％，例如45％、46％、47％、48％、49％或50％等。Preferably, the porosity of the membrane is greater than or equal to 45%, such as 45%, 46%, 47%, 48%, 49% or 50%, etc.
孔隙率大于或等于45％有利于锂离子电容器高倍率充放电，如果隔膜的孔隙率小于45％，会导致高倍率下，充放电性能下降。A porosity greater than or equal to 45% is conducive to high-rate charge and discharge of lithium-ion capacitors. If the porosity of the separator is less than 45%, the charge-discharge performance will decrease at high rates.
优选地，所述隔膜的透气度小于或等于200s/100mL，例如200s/100mL、180s/100mL、150s/100mL、130s/100mL或100s/100mL等。Preferably, the air permeability of the membrane is less than or equal to 200s/100mL, such as 200s/100mL, 180s/100mL, 150s/100mL, 130s/100mL or 100s/100mL, etc.
优选地，所述电解液包括六氟磷酸锂、溶剂和添加剂。Preferably, the electrolyte includes lithium hexafluorophosphate, a solvent and additives.
优选地，所述六氟磷酸锂的摩尔浓度为0.8～1.5mol/L，例如0.8mol/L、0.9mol/L、1mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L或1.5mol/L等。Preferably, the molar concentration of the lithium hexafluorophosphate is 0.8-1.5 mol/L, such as 0.8 mol/L, 0.9 mol/L, 1 mol/L, 1.1 mol/L, 1.2 mol/L, 1.3 mol/L, 1.4 mol/L L or 1.5mol/L, etc.
优选地，所述溶剂包括碳酸乙烯酯、碳酸甲乙酯、乙酸乙酯和丙酸乙酯。Preferably, the solvent includes ethylene carbonate, ethyl methyl carbonate, ethyl acetate and ethyl propionate.
以溶剂和添加剂的质量总和为100％计：Based on the sum of the mass of solvent and additives as 100%:
优选地，所述碳酸乙烯酯在所述电解液中的质量分数为7～13wt％，例如7wt％、8wt％、9wt％、10wt％、11wt％、12wt％或13wt％等。Preferably, the mass fraction of the ethylene carbonate in the electrolyte is 7-13 wt %, for example, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt % or 13 wt %, etc.
优选地，所述碳酸甲乙酯在所述电解液中的质量分数为7～13wt％，例如7wt％、8wt％、9wt％、10wt％、11wt％、12wt％或13wt％等。Preferably, the mass fraction of the ethyl methyl carbonate in the electrolyte is 7-13 wt %, for example, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt % or 13 wt %, etc.
优选地，所述乙酸乙酯在所述电解液中的质量分数为70～80wt％，例如70wt％、71wt％、72wt％、73wt％、74wt％、75wt％、76wt％、77wt％、78wt％、79wt％或80wt％等。Preferably, the mass fraction of the ethyl acetate in the electrolyte is 70-80wt%, such as 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt% , 79wt% or 80wt%, etc.
优选地，所述丙酸乙酯在所述电解液中的质量分数为1～5wt％，例如1wt％、2wt％、3wt％、4wt％或5wt％等。Preferably, the mass fraction of the ethyl propionate in the electrolyte is 1 to 5 wt %, for example, 1 wt %, 2 wt %, 3 wt %, 4 wt %, or 5 wt %.
优选地，所述添加剂包括碳酸亚乙烯酯、氟代碳酸乙烯酯和硫酸乙烯酯。Preferably, the additives include vinylene carbonate, fluoroethylene carbonate and vinyl sulfate.
优选地，所述碳酸亚乙烯酯在所述电解液中的质量分数为1～2wt％，例如1wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％或2wt％等。Preferably, the mass fraction of the vinylene carbonate in the electrolyte is 1-2wt%, for example, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt% %, 1.7 wt %, 1.8 wt %, 1.9 wt % or 2 wt %, etc.
优选地，所述氟代碳酸乙烯酯在所述电解液中的质量分数为0.5～1.5wt％，例如0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％或1.5wt％等。Preferably, the mass fraction of the fluoroethylene carbonate in the electrolyte is 0.5 to 1.5 wt %, such as 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.1 wt %, 1.2 wt %, 1.3 wt %, 1.4 wt % or 1.5 wt %, etc.
优选地，所述硫酸乙烯酯在所述电解液中的质量分数为0.5～1.5wt％，例如0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％或1.5wt％等。Preferably, the mass fraction of the vinyl sulfate in the electrolyte is 0.5-1.5wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt% %, 1.2 wt %, 1.3 wt %, 1.4 wt % or 1.5 wt %, etc.
优选地，所述电解液的室温离子电导率大于或等于12mS/cm，12mS/cm、13mS/cm、14mS/cm、15mS/cm或16mS/cm等。Preferably, the room temperature ionic conductivity of the electrolyte is greater than or equal to 12 mS/cm, 12 mS/cm, 13 mS/cm, 14 mS/cm, 15 mS/cm or 16 mS/cm, and the like.
第二方面，本发明提供一种如第一方面所述的锂离子电容器的制备方法，所述制备方法包括：In a second aspect, the present invention provides a preparation method of a lithium ion capacitor as described in the first aspect, the preparation method comprising:
将正极、负极与隔膜叠加，形成叠加电芯；将所述叠加电芯注入电解液，再经过抽气、封口，得到所述锂离子电容器；Superimposing the positive electrode, the negative electrode and the diaphragm to form a superimposed battery cell; injecting the superimposed battery core into the electrolyte, and then exhausting and sealing to obtain the lithium ion capacitor;
所述正极的制备方法包括：将磷酸铁锂、双电层材料、导电剂和粘结剂混合制成浆料，将所述浆料涂覆在正极集流体上，干燥，辊压，得到所述正极；The preparation method of the positive electrode includes: mixing lithium iron phosphate, an electric double layer material, a conductive agent and a binder to prepare a slurry, coating the slurry on the positive electrode current collector, drying, and rolling to obtain the obtained slurry. the positive electrode;
所述负极的制备方法包括：将晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂混合制成浆料，涂覆在负极集流体上，干燥，辊压得到所述负极。The preparation method of the negative electrode includes: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder to prepare a slurry, coating the negative electrode current collector, drying, and rolling to obtain the negative electrode.
本发明所制备的锂离子电容器，本发明通过复配高电导率高倍率具有双电层特性的材料来改善磷酸铁锂正极锂离子迁移速率低的问题，提高了正极的倍率性能和低温性能，选用了晶面间距d002较大的碳材料制备负极材料来提高负极的倍率和低温性能，从而提高了使用磷酸铁锂锂离子电容器的倍率性能和低温性能。In the lithium ion capacitor prepared by the present invention, the present invention improves the problem of low lithium ion migration rate of the lithium iron phosphate positive electrode by compounding materials with high conductivity and high rate with electric double layer characteristics, and improves the rate performance and low temperature performance of the positive electrode, A carbon material with a large interplanar spacing d002 is selected to prepare the negative electrode material to improve the rate and low temperature performance of the negative electrode, thereby improving the rate performance and low temperature performance of the lithium iron phosphate lithium ion capacitor.
优选地，对所述正极和负极分别进行裁切后得到正极片和负极片，再与隔膜进行叠加。Preferably, the positive electrode and the negative electrode are respectively cut to obtain a positive electrode sheet and a negative electrode sheet, which are then stacked with the separator.
优选地，所述叠加操作的仪器为自动叠片机。Preferably, the apparatus for the stacking operation is an automatic stacker.
优选地，所述叠加电芯两侧各放置一片金属锂片。Preferably, one metal lithium sheet is placed on each side of the superimposed battery cell.
优选地，所述注入电解液操作前对叠加电芯进行高温干燥，超声焊接和顶侧封操作。Preferably, high temperature drying, ultrasonic welding and top and side sealing operations are performed on the superposed cells before the operation of injecting the electrolyte.
优选地，所述辊压后的正极的压实密度为1.3～2.2g/cm 3，例如1.3g/cm 3、1.5g/cm 3、1.8g/cm 3、2g/cm 3、2.1g/cm 3或2.2g/cm 3等。 Preferably, the compacted density of the rolled positive electrode is 1.3-2.2 g/cm 3 , for example, 1.3 g/cm 3 , 1.5 g/cm 3 , 1.8 g/cm 3 , 2 g/cm 3 , 2.1 g/cm 3 . cm 3 or 2.2g/cm 3 etc.
控制正极材料的压实密度在1.3～2.2g/cm 3对于倍率性能和低温性能至关重要。 Controlling the compaction density of cathode materials in the range of 1.3 to 2.2 g/ cm3 is crucial for rate performance and low temperature performance.
优选地，所述正极集流体的厚度为15～30μm，例如15μm、18μm、20μm、23μm、25μm、28μm或30μm等。Preferably, the thickness of the positive electrode current collector is 15-30 μm, for example, 15 μm, 18 μm, 20 μm, 23 μm, 25 μm, 28 μm, or 30 μm.
优选地，所述正极集流体包括表面涂有导电涂层的铝箔、铝网或经过表面处理的铝箔中的任意一种或至少两种的组合。Preferably, the positive electrode current collector comprises any one or a combination of at least two of aluminum foil, aluminum mesh or surface-treated aluminum foil coated with conductive coating on the surface.
优选地，所述正极的正极面电阻小于或等于10Ω·cm 2，例如10Ω·cm 2、9Ω·cm 2、8Ω·cm 2、7Ω·cm 2、6Ω·cm 2或5Ω·cm 2等。 Preferably, the positive surface resistance of the positive electrode is less than or equal to 10Ω·cm 2 , such as 10Ω·cm 2 , 9Ω·cm 2 , 8Ω·cm 2 , 7Ω·cm 2 , 6Ω·cm 2 or 5Ω·cm 2 , etc.
控制所述正极的正极面电阻在上述数值范围对于锂离子电容器倍率性能至关重要。Controlling the positive surface resistance of the positive electrode within the above-mentioned range is crucial for the rate performance of the lithium ion capacitor.
优选地，所述辊压后的负极的压实密度为0.8～1.4g/cm 3，例如0.8g/cm 3、0.9g/cm 3、1g/cm 3、1.1g/cm 3、1.2g/cm 3、1.3g/cm 3或1.4g/cm 3等。 Preferably, the compaction density of the negative electrode after rolling is 0.8-1.4 g/cm 3 , for example, 0.8 g/cm 3 , 0.9 g/cm 3 , 1 g/cm 3 , 1.1 g/cm 3 , 1.2 g/cm 3 . cm 3 , 1.3g/cm 3 or 1.4g/cm 3 etc.
控制负极材料的压实密度对于倍率性能和低温性能至关重要。Controlling the compaction density of anode materials is critical for rate capability and low temperature performance.
优选地，所述负极集流体的厚度为10～25μm，例如10μm、12μm、15μm、18μm、20μm、23μm或25μm等。Preferably, the thickness of the negative electrode current collector is 10-25 μm, for example, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 23 μm, or 25 μm.
优选地，所述负极集流体包括表面涂有导电涂层的铜箔、铜网或经过表面处理的铜箔中的任意一种或至少两种的组合。Preferably, the negative electrode current collector comprises any one or a combination of at least two of copper foil, copper mesh or surface-treated copper foil coated with a conductive coating on the surface.
优选地，所述负极的负极面电阻小于或等于3Ω·cm 2，例如3Ω·cm 2、2.5Ω·cm 2、2Ω·cm 2或1.5Ω·cm 2等。 Preferably, the negative surface resistance of the negative electrode is less than or equal to 3Ω·cm 2 , such as 3Ω·cm 2 , 2.5Ω·cm 2 , 2Ω·cm 2 or 1.5Ω·cm 2 , and the like.
控制所述负极的负极面电阻在上述数值范围对于锂离子电容器倍率性能至关重要。Controlling the negative surface resistance of the negative electrode within the above-mentioned range is crucial for the rate performance of the lithium ion capacitor.
优选地，所述负极比容量和正极比容量的比值N/P比为2～3.5，例如2、2.2、2.5、2.8、3、3.3或3.5等。Preferably, the ratio N/P ratio of the specific capacity of the negative electrode and the specific capacity of the positive electrode is 2˜3.5, such as 2, 2.2, 2.5, 2.8, 3, 3.3 or 3.5, etc.
作为优选的技术方案，所述锂离子电容器的制备方法包括：As a preferred technical solution, the preparation method of the lithium ion capacitor includes:
将正极、负极分别裁切成正极片和负极片，与隔膜在自动叠片机上叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入所述电解液、抽气、封口，得到所述锂离子电容器；Cut the positive and negative electrodes into positive and negative electrode sheets respectively, and stack them with the separator on an automatic stacking machine to form a battery cell, place a metal lithium sheet on each side of the battery cell, dry at high temperature, ultrasonic welding, top-side sealing, injection The electrolyte, pumping, and sealing to obtain the lithium ion capacitor;
所述正极的制备方法包括：将磷酸铁锂、多孔炭、导电剂和粘结剂按照(45～90):(5～45):(3～10):(2～10)的质量比混合制成浆料，涂覆在厚度为15～30μm的正极集流体上，干燥，辊压，压实密度为1.3～2.2g/cm 3，得到所述正极，所述正极的正极面电阻小于或等于10Ω·cm 2； The preparation method of the positive electrode comprises: mixing lithium iron phosphate, porous carbon, conductive agent and binder according to the mass ratio of (45-90):(5-45):(3-10):(2-10) Slurry is made, coated on a positive electrode current collector with a thickness of 15-30 μm, dried, rolled, and compacted at a density of 1.3-2.2 g/cm 3 to obtain the positive electrode whose positive surface resistance of the positive electrode is less than or is equal to 10Ω·cm 2 ;
所述负极的制备方法包括：将晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂以(80～98):(0～10):(2～10)的质量比混合制成浆料，涂覆在厚度为10～25μm的负极集流体上，干燥，辊压得到所述负极，负极的负极面电阻小于或等于3Ω·cm 2。 The preparation method of the negative electrode includes: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder in a mass ratio of (80-98):(0-10):(2-10) Slurry is formed, coated on a negative electrode current collector with a thickness of 10-25 μm, dried, and rolled to obtain the negative electrode, and the negative electrode surface resistance of the negative electrode is less than or equal to 3Ω·cm 2 .
第三方面，本发明还提供一种如第一方面所述的锂离子电容器的用途，所述用途包括将所述的锂离子电容器用作储能器件。In a third aspect, the present invention also provides a use of the lithium ion capacitor according to the first aspect, the use comprising using the lithium ion capacitor as an energy storage device.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明通过优选合适参数的正负极活性物质，优化材料复配和配比，降低集流体内阻，优选高孔隙率低透气度的隔膜，提高电解液在常温和低温下的电导率，对压实密度和面电阻进行精确控制，提高了极片的导电能力和电解液的浸润性，减小了极化，从而提高了使用磷酸铁锂锂离子电容器的倍率性能和低温性能。通过使用本发明技术制备的锂离子电容器，本发明制备的化学电源具有高倍率(5C容量是1C的96％以上)和优异的低温性能(-20℃是25℃的79％以上)，同时还具有高安全、低成本的特点，为船用和军工领域的应用提供保障，有利于扩大锂离子电容器的市场占有率。In the present invention, the positive and negative active materials with suitable parameters are optimized, the material compounding and proportioning are optimized, the internal resistance of the current collector is reduced, the diaphragm with high porosity and low air permeability is preferred, and the electrical conductivity of the electrolyte at room temperature and low temperature is improved. The compaction density and surface resistance are precisely controlled, which improves the conductivity of the pole piece and the wettability of the electrolyte, and reduces the polarization, thereby improving the rate performance and low temperature performance of lithium iron phosphate lithium ion capacitors. By using the lithium ion capacitor prepared by the technology of the present invention, the chemical power source prepared by the present invention has high rate (5C capacity is more than 96% of 1C) and excellent low temperature performance (-20°C is more than 79% of 25°C), and also With the characteristics of high safety and low cost, it provides guarantee for applications in the marine and military fields, and is conducive to expanding the market share of lithium-ion capacitors.
附图说明Description of drawings
图1为实施例1中提供的锂离子电容器在1C和5C的放电曲线。FIG. 1 shows the discharge curves of the lithium ion capacitor provided in Example 1 at 1C and 5C.
图2为实施例2中提供的锂离子电容器在25℃和-20℃条件下的5C放电曲线。2 is a 5C discharge curve of the lithium ion capacitor provided in Example 2 at 25°C and -20°C.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
实施例1Example 1
本实施例提供一种锂离子电容器，所述锂离子电容器包括正极、负极、PET无纺布隔膜和电解液；所述正极的材料包括磷酸铁锂、活性炭、以炭黑和导电石墨作为导电剂、以聚偏氟乙烯作为粘结剂；所述负极的材料包括晶面间距d002为0.382nm的硬碳材料、以炭黑和碳纳米管作为导电剂、以聚偏氟乙烯作为粘结剂；This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a PET non-woven separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and conductive graphite as conductive agents , using polyvinylidene fluoride as a binder; the material of the negative electrode includes a hard carbon material with a crystal plane spacing d002 of 0.382nm, carbon black and carbon nanotubes as a conductive agent, and polyvinylidene fluoride as a binder;
其中，所述电解液的室温离子电导率为14mS/cm，所述电解液中包括1.1mol/L的六氟磷酸锂，8wt％的碳酸乙烯酯，10wt％的碳酸甲乙酯，76wt％的乙酸乙酯和3wt％的丙酸乙酯，1wt％的碳酸亚乙烯酯，1wt％的氟代碳酸乙烯酯和1wt％的硫酸乙烯酯。(上述重量分数以添加剂和溶剂的质量总和为100％计)。Wherein, the room temperature ionic conductivity of the electrolyte solution is 14mS/cm, and the electrolyte solution includes 1.1mol/L lithium hexafluorophosphate, 8wt% ethylene carbonate, 10wt% ethyl methyl carbonate, 76wt% ethyl acetate and 3 wt % of ethyl propionate, 1 wt % of vinylene carbonate, 1 wt % of fluoroethylene carbonate and 1 wt % of vinyl sulfate. (The above weight fractions are based on the total mass of additives and solvents as 100%).
所述锂离子电容器的制备方法如下：The preparation method of the lithium ion capacitor is as follows:
a.正极制备：将D50为6μm的磷酸铁锂、比表面积为1600m 2/g的活性炭为双电层材料、炭黑、导电石墨和聚偏氟乙烯按照质量比86:5:3.5:1.5:4混合制成浆料，均匀涂覆在厚度为20μm的涂炭铝箔上，干燥，辊压，压实密度为2.05g/cm 3，得到正极材料，控制正极面电阻不超过3Ω·cm 2。 a. Preparation of positive electrode: use lithium iron phosphate with D50 of 6 μm and activated carbon with specific surface area of 1600 m 2 /g as electric double layer material, carbon black, conductive graphite and polyvinylidene fluoride according to the mass ratio of 86:5:3.5:1.5: 4. Mixed to make slurry, uniformly coated on carbon-coated aluminum foil with a thickness of 20 μm, dried, rolled, and compacted at a density of 2.05 g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled not to exceed 3Ω·cm 2 .
b.负极制备：将D50为5μm，d002为0.382nm的硬碳材料、炭黑、碳纳米管和聚偏氟乙烯按照质量比91:1.5:0.5:7混合制成浆料，均匀涂覆在厚度为12μm的涂炭铜箔上，干燥，辊压，压实密度为1.0g/cm 3，得到负极材料，控制负极面电阻不超过1Ω·cm 2，负极与正极的容量比为2。 b. Negative electrode preparation: Mix hard carbon material with D50 of 5μm and d002 of 0.382nm, carbon black, carbon nanotubes and polyvinylidene fluoride in a mass ratio of 91:1.5:0.5:7 to make a slurry, which is uniformly coated on the The carbon-coated copper foil with a thickness of 12 μm was dried, rolled, and the compacted density was 1.0 g /cm 3 to obtain a negative electrode material.
c.隔膜为PET无纺布隔膜，孔隙率54％，透气度11s/100mL；c. The diaphragm is a PET non-woven diaphragm with a porosity of 54% and an air permeability of 11s/100mL;
d.电解液由1.1mol/L的六氟磷酸锂，8wt％的碳酸乙烯酯，10wt％的碳酸甲乙酯，75wt％的乙酸乙酯和3wt％的丙酸乙酯，1wt％的碳酸亚乙烯酯，1wt％的氟代碳酸乙烯酯和 1wt％的硫酸乙烯酯组成，(上述重量分数以电解液为100％计)室温离子电导率14mS/cm；d. The electrolyte consists of 1.1mol/L lithium hexafluorophosphate, 8wt% ethylene carbonate, 10wt% methyl ethyl carbonate, 75wt% ethyl acetate and 3wt% ethyl propionate, 1wt% vinylene carbonate, It is composed of 1wt% of fluoroethylene carbonate and 1wt% of ethylene sulfate, (the above weight fraction is based on the electrolyte as 100%) and the room temperature ionic conductivity is 14mS/cm;
e.锂离子电容器制备：将正极、负极裁切成的极片，与PET无纺布隔膜在自动叠片机上以Z型叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入电解液、抽气、封口等步骤得到最终的使用磷酸铁锂的软包装锂离子电容器。e. Preparation of lithium ion capacitors: The positive and negative pole pieces are cut into pole pieces, and the PET non-woven fabric separator is stacked on an automatic laminating machine in a Z shape to form a battery cell, and a metal lithium piece is placed on each side of the battery core. High temperature drying, ultrasonic welding, top and side sealing, electrolyte injection, air extraction, sealing and other steps to obtain the final flexible packaging lithium ion capacitor using lithium iron phosphate.
从图1中可以得出锂离子电容器5C的放电容量是1C放电容量的96.7％。It can be concluded from Fig. 1 that the discharge capacity of the lithium-ion capacitor 5C is 96.7% of the discharge capacity of 1C.
实施例2Example 2
本实施例提供一种锂离子电容器，所述锂离子电容器包括正极、负极、纤维素隔膜和电解液；所述正极的材料包括磷酸铁锂、介孔碳、以炭黑和气相生长碳纤维作为导电剂、以聚偏氟乙烯作为粘结剂；所述负极的材料包括晶面间距d002为0.352nm的软碳材料、以炭黑和石墨烯作为导电剂、以聚丙烯酸酯作为粘结剂；This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a cellulose separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, mesoporous carbon, carbon black and vapor-grown carbon fiber as conductive materials using polyvinylidene fluoride as a binder; the material of the negative electrode includes a soft carbon material with a crystal plane spacing d002 of 0.352nm, carbon black and graphene as a conductive agent, and polyacrylate as a binder;
其中，所述电解液的室温离子电导率为12.5mS/cm，所述电解液中包括1.05mol/L的六氟磷酸锂，10wt％的碳酸乙烯酯，10wt％的碳酸甲乙酯，75wt％的乙酸乙酯和3wt％的丙酸乙酯，1wt％的碳酸亚乙烯酯，0.5wt％的氟代碳酸乙烯酯和0.5wt％的硫酸乙烯酯。(上述重量分数以添加剂和溶剂的质量总和为100％计)。Wherein, the room temperature ionic conductivity of the electrolyte solution is 12.5mS/cm, and the electrolyte solution includes 1.05mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 10wt% ethyl methyl carbonate, 75wt% ethyl acetate ester and 3 wt % ethyl propionate, 1 wt % vinylene carbonate, 0.5 wt % fluoroethylene carbonate and 0.5 wt % vinyl sulfate. (The above weight fractions are based on the total mass of additives and solvents as 100%).
所述锂离子电容器的制备方法如下：The preparation method of the lithium ion capacitor is as follows:
a.正极制备：将D50为7μm的磷酸铁锂、比表面积为1800m 2/g的介孔碳为双电层材料、炭黑、气相生长碳纤维和聚偏氟乙烯按照质量比85:7:3:1:4混合制成浆料，均匀涂覆在厚度为21μm的腐蚀铝箔上，干燥，辊压，压实密度为2g/cm 3，得到正极材料，控制正极面电阻不超过2.5Ω·cm 2。 a. Preparation of positive electrode: Lithium iron phosphate with D50 of 7 μm, mesoporous carbon with specific surface area of 1800 m 2 /g as electric double layer material, carbon black, vapor-grown carbon fiber and polyvinylidene fluoride in a mass ratio of 85:7:3 :1:4 mixed into slurry, uniformly coated on 21μm-thick corroded aluminum foil, dried, rolled, and compacted at a density of 2g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled not to exceed 2.5Ω·cm 2 .
b.负极制备：将D50为6μm，d002为0.352nm的软碳、炭黑、石墨烯和聚丙烯酸酯按照质量比92:2:0.5:5.5混合制成浆料，均匀涂覆在厚度为12μm的涂炭铜箔上，干燥，辊压，压实密度为1.3g/cm 3，得到负极材料，控制负极面电阻不超过1.2Ω·cm 2，负极与正极的容量比为2.5。 b. Negative electrode preparation: Mix soft carbon, carbon black, graphene and polyacrylate with a D50 of 6 μm and a d002 of 0.352 nm according to the mass ratio of 92:2:0.5:5.5 to make a slurry, which is uniformly coated on a thickness of 12 μm The carbon-coated copper foil was dried, rolled, and the compacted density was 1.3 g /cm 3 to obtain a negative electrode material.
c.隔膜为纤维素隔膜，孔隙率70％，透气度7s/100mL；c. The diaphragm is a cellulose diaphragm with a porosity of 70% and an air permeability of 7s/100mL;
d.电解液由1.05mol/L的六氟磷酸锂，10wt％的碳酸乙烯酯，10wt％的碳酸甲乙酯，75wt％的乙酸乙酯和3wt％的丙酸乙酯，1wt％的碳酸亚乙烯酯，0.5wt％的氟代碳酸乙烯酯和0.5wt％的硫酸乙烯酯组成，(上述重量分数以电解液为100％计)室温离子电导率12.5mS/cm；d. The electrolyte consists of 1.05mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 10wt% methyl ethyl carbonate, 75wt% ethyl acetate and 3wt% ethyl propionate, 1wt% vinylene carbonate, It is composed of 0.5wt% of fluoroethylene carbonate and 0.5wt% of ethylene sulfate, (the above weight fraction is based on the electrolyte solution as 100%) and the room temperature ionic conductivity is 12.5mS/cm;
e.锂离子电容器制备：将正极、负极裁切成极片，与纤维素隔膜在自动叠片机上以Z型叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入电解液、抽气、封口等步骤得到最终的使用磷酸铁锂的软包装锂离子电容器。e. Preparation of lithium ion capacitors: Cut the positive and negative electrodes into pole pieces, and stack them with the cellulose separator in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
从图2中可以得出锂离子电容器在-20℃下的放电容量是25℃放电容量的82.2％。From Figure 2, it can be concluded that the discharge capacity of the lithium-ion capacitor at -20°C is 82.2% of the discharge capacity at 25°C.
实施例3Example 3
本实施例提供一种锂离子电容器，所述锂离子电容器包括正极、负极、PP陶瓷隔膜和电解液；所述正极的材料包括磷酸铁锂、活性炭、以炭黑和导电石墨作为导电剂、以聚偏氟乙烯作为粘结剂；所述负极的材料包括晶面间距d002为0.38nm的硬碳材料、以炭黑、碳纳米管作为导电剂、以羧甲基纤维素钠和丁苯橡胶作为粘结剂；This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a PP ceramic separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and conductive graphite as conductive agents, and Polyvinylidene fluoride is used as a binder; the material of the negative electrode includes a hard carbon material with a crystal plane spacing d002 of 0.38 nm, carbon black and carbon nanotubes as conductive agents, sodium carboxymethyl cellulose and styrene-butadiene rubber as binder;
其中，所述电解液的室温离子电导率为14mS/cm，所述电解液中包括1mol/L的六氟磷酸锂，10wt％的碳酸乙烯酯，7wt％的碳酸甲乙酯，78wt％的乙酸乙酯和2wt％的丙酸乙 酯，1.5wt％的碳酸亚乙烯酯，1wt％的氟代碳酸乙烯酯和0.5wt％的硫酸乙烯酯。(上述重量分数以添加剂和溶剂的质量总和为100％计)。Wherein, the room temperature ionic conductivity of the electrolyte solution is 14mS/cm, and the electrolyte solution includes 1mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 7wt% ethyl methyl carbonate, 78wt% ethyl acetate and 2 wt% ethyl propionate, 1.5 wt% vinylene carbonate, 1 wt% fluoroethylene carbonate and 0.5 wt% vinyl sulfate. (The above weight fractions are based on the total mass of additives and solvents as 100%).
所述锂离子电容器的制备方法如下：The preparation method of the lithium ion capacitor is as follows:
a.正极制备：将D50为3μm的磷酸铁锂、比表面积为2240m 2/g的活性炭为双电层材料、炭黑、导电石墨和聚偏氟乙烯按照质量比70:20:4:1:5混合制成浆料，均匀涂覆在厚度为22μm的腐蚀铝箔上，干燥，辊压，压实密度为1.8g/cm 3，得到正极材料，控制正极面电阻不超过3.5Ω·cm 2。 a. Positive electrode preparation: The D50 of 3μm lithium iron phosphate, the activated carbon with a specific surface area of 2240m 2/ g is used as the electric double layer material, carbon black, conductive graphite and polyvinylidene fluoride according to the mass ratio of 70:20:4:1: 5. Mixed to make a slurry, uniformly coated on 22μm thick corroded aluminum foil, dried, rolled, and compacted to a density of 1.8g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled to be no more than 3.5Ω·cm 2 .
b.负极制备：将D50为9μm，d002为0.38nm的硬碳材料、炭黑、碳纳米管、羧甲基纤维素钠和丁苯橡胶按照质量比90:1:1:4:4混合制成浆料，均匀涂覆在厚度为14μm的涂炭铜箔上，干燥，辊压，压实密度为1.5g/cm 3，得到负极材料，控制负极面电阻不超过1.5Ω·cm 2，负极与正极的容量比为3.5。 b. Preparation of negative electrode: Mix hard carbon material with D50 of 9 μm and d002 of 0.38 nm, carbon black, carbon nanotubes, sodium carboxymethyl cellulose and styrene-butadiene rubber in a mass ratio of 90:1:1:4:4. A slurry was formed, which was uniformly coated on a carbon-coated copper foil with a thickness of 14 μm, dried, rolled, and compacted to a density of 1.5 g/cm 3 to obtain a negative electrode material, and the surface resistance of the negative electrode was controlled not to exceed 1.5Ω·cm 2 . The capacity ratio of the positive electrode was 3.5.
c.隔膜为PP陶瓷隔膜，孔隙率50％，透气度187s/100mL；c. The diaphragm is a PP ceramic diaphragm, with a porosity of 50% and an air permeability of 187s/100mL;
d.电解液由1mol的六氟磷酸锂，10wt％碳酸乙烯酯，7wt％碳酸甲乙酯，78wt％乙酸乙酯和2wt％丙酸乙酯，1.5wt％碳酸亚乙烯酯，1wt％氟代碳酸乙烯酯和0.5wt％硫酸乙烯酯组成，(上述质量分数以电解液为100％计)室温离子电导率14mS/cm；d. The electrolyte consists of 1mol lithium hexafluorophosphate, 10wt% ethylene carbonate, 7wt% methyl ethyl carbonate, 78wt% ethyl acetate and 2wt% ethyl propionate, 1.5wt% vinylene carbonate, 1wt% fluoroethylene carbonate It is composed of 0.5wt% vinyl sulfate, (the above mass fraction is based on the electrolyte as 100%), and the room temperature ionic conductivity is 14mS/cm;
e.锂离子电容器制备：将正极、负极裁切成极片，与PP陶瓷隔膜在自动叠片机上以Z型叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入电解液、抽气、封口等步骤得到最终的使用磷酸铁锂的软包装锂离子电容器。e. Preparation of lithium ion capacitors: Cut the positive and negative electrodes into pole pieces, and stack them with the PP ceramic diaphragm in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the battery cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
实施例4Example 4
本实施例提供一种锂离子电容器，所述锂离子电容器包括正极、负极、纤维素隔膜和电解液；所述正极的材料包括磷酸铁锂、活性炭、以炭黑和气相生长碳纤维作为导电剂、以聚丙烯酸作为粘结剂；所述负极的材料包括晶面间距d002为0.35nm的软碳材料、以炭黑和气相生长碳纤维作为导电剂、以聚偏氟乙烯作为粘结剂；This embodiment provides a lithium ion capacitor, the lithium ion capacitor includes a positive electrode, a negative electrode, a cellulose separator and an electrolyte; the material of the positive electrode includes lithium iron phosphate, activated carbon, carbon black and vapor-grown carbon fiber as conductive agents, Using polyacrylic acid as a binder; the material of the negative electrode includes a soft carbon material with a crystal plane spacing d002 of 0.35 nm, carbon black and vapor-grown carbon fiber as a conductive agent, and polyvinylidene fluoride as a binder;
其中，所述电解液的室温离子电导率为12mS/cm，所述电解液中包括1.2mol/L的六氟磷酸锂，10wt％的碳酸乙烯酯，13wt％的碳酸甲乙酯，70wt％的乙酸乙酯和3.5wt％的丙酸乙酯，1.5wt％的碳酸亚乙烯酯，1wt％的氟代碳酸乙烯酯和1wt％的硫酸乙烯酯。((上述重量分数以添加剂和溶剂的质量总和为100％计)。Wherein, the room temperature ionic conductivity of the electrolyte solution is 12mS/cm, and the electrolyte solution includes 1.2mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 13wt% ethyl methyl carbonate, 70wt% ethyl acetate and 3.5 wt% ethyl propionate, 1.5 wt% vinylene carbonate, 1 wt% fluoroethylene carbonate and 1 wt% vinyl sulfate. ((The above weight fraction is based on the total mass of additives and solvents as 100%).
所述锂离子电容器的制备方法如下：The preparation method of the lithium ion capacitor is as follows:
a.正极制备：将D50为1.5μm的磷酸铁锂、比表面积为1800m 2/g的活性炭为双电层材料、炭黑、气相生长碳纤维和聚丙烯酸按照质量比80:10:2.5:2.5:5混合制成浆料，均匀涂覆在厚度为20μm的腐蚀铝箔上，干燥，辊压，压实密度为2g/cm 3，得到正极材料，控制正极面电阻不超过4Ω·cm 2。 a. Preparation of positive electrode: Lithium iron phosphate with D50 of 1.5 μm and activated carbon with specific surface area of 1800 m 2 /g are used as electric double layer material, carbon black, vapor grown carbon fiber and polyacrylic acid according to the mass ratio of 80:10:2.5:2.5: 5. Mixed to make slurry, uniformly coated on 20μm thick corroded aluminum foil, dried, rolled, and compacted to a density of 2g/cm 3 to obtain a positive electrode material, and the surface resistance of the positive electrode was controlled not to exceed 4Ω·cm 2 .
b.负极制备：将D50为8μm，d002为0.35nm的软碳材料、炭黑、碳纳米管和聚偏氟乙烯按照质量比93:1:1:5混合制成浆料，均匀涂覆在厚度为12μm的涂炭铜箔上，干燥，辊压，压实密度为1.25g/cm 3，得到负极材料，控制负极面电阻不超过0.8Ω·cm 2，负极与正极的容量比为2.5。 b. Negative electrode preparation: Mix soft carbon material with D50 of 8 μm and d002 of 0.35 nm, carbon black, carbon nanotubes and polyvinylidene fluoride in a mass ratio of 93:1:1:5 to make a slurry, which is uniformly coated on the The carbon-coated copper foil with a thickness of 12 μm was dried, rolled, and the compacted density was 1.25 g /cm 3 to obtain a negative electrode material.
c.隔膜为芳纶隔膜，孔隙率54％，透气度5s/100mL；c. The diaphragm is an aramid diaphragm, with a porosity of 54% and an air permeability of 5s/100mL;
d.电解液由1.2mol/L的六氟磷酸锂，10wt％碳酸乙烯酯，13wt％碳酸甲乙酯，70wt％乙酸乙酯和3.5wt％丙酸乙酯，1.5wt％碳酸亚乙烯酯，1wt％氟代碳酸乙烯酯和 1wt％硫酸乙烯酯组成，(上述重量分数以电解液为100％计)室温离子电导率12mS/cm；d. The electrolyte consists of 1.2mol/L lithium hexafluorophosphate, 10wt% ethylene carbonate, 13wt% methyl ethyl carbonate, 70wt% ethyl acetate and 3.5wt% ethyl propionate, 1.5wt% vinylene carbonate, 1wt% fluorine It is composed of ethylene carbonate and 1wt% ethylene sulfate, (the above weight fraction is based on the electrolyte as 100%), and the ionic conductivity at room temperature is 12mS/cm;
e.锂离子电容器制备：将正极、负极裁切成极片，与芳纶隔膜在自动叠片机上以Z型叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入电解液、抽气、封口等步骤得到最终的使用磷酸铁锂的软包装锂离子电容器。e. Preparation of lithium ion capacitors: Cut the positive and negative electrodes into pole pieces, and stack them with the aramid membrane in a Z shape on an automatic laminating machine. Place a metal lithium piece on each side of the battery cell, and dry it at high temperature. Ultrasonic welding, top-side sealing, electrolyte injection, gas extraction, sealing and other steps are performed to obtain the final flexible packaging lithium-ion capacitor using lithium iron phosphate.
实施例5Example 5
本实施例与实施例1的区别为：本实施例中正极制备过程中将D50为6μm的磷酸铁锂、比表面积为1600m 2/g的活性炭为双电层材料、炭黑、导电石墨和聚偏氟乙烯按照质量比调整为91:4:2.5:1.5:1混合制成浆料。 The difference between this embodiment and Embodiment 1 is: in the preparation process of the positive electrode in this embodiment, lithium iron phosphate with D50 of 6 μm and activated carbon with a specific surface area of 1600 m 2 /g are used as electric double layer material, carbon black, conductive graphite and polymer Vinylidene fluoride was adjusted to a mass ratio of 91:4:2.5:1.5:1 and mixed to make a slurry.
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
实施例6Example 6
本实施例与实施例1的区别为：本实施例制备负极材料过程中，将D50为5μm，d002为0.382nm的硬碳、炭黑、碳纳米管和聚偏氟乙烯按照质量比调整为98.5:0.3:0.2:1混合制成浆料。The difference between this example and Example 1 is: in the process of preparing the negative electrode material in this example, the hard carbon, carbon black, carbon nanotube and polyvinylidene fluoride with D50 of 5 μm and d002 of 0.382 nm were adjusted to 98.5 by mass ratio. :0.3:0.2:1 mixed to make slurry.
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
实施例7Example 7
本实施例与实施例1的区别为：本实施例中正极的正极面电阻为6Ω·cm 2。 The difference between this embodiment and Embodiment 1 is that the positive electrode surface resistance of the positive electrode in this embodiment is 6Ω·cm 2 .
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
实施例8Example 8
本实施例与实施例1的区别为：本实施例中负极的负极面电阻为4Ω·cm 2。 The difference between this embodiment and Embodiment 1 is that the negative electrode sheet resistance of the negative electrode in this embodiment is 4Ω·cm 2 .
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
实施例9Example 9
本实施例与实施例1的区别为：本实施例的正极材料中的磷酸铁锂的D50为20μm。The difference between this embodiment and Embodiment 1 is that the D50 of the lithium iron phosphate in the positive electrode material of this embodiment is 20 μm.
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
实施例10Example 10
本实施例与实施例1的区别为：本对比例的负极材料中的硬碳材料的晶面间距d002为0.37nm。The difference between this example and Example 1 is that the interplanar spacing d002 of the hard carbon material in the negative electrode material of this comparative example is 0.37 nm.
对比例1Comparative Example 1
本对比例与实施例1的区别为：本对比例在制备正极过程中，不添加活性炭材料，仅为磷酸铁锂这一种活性物质。The difference between this comparative example and Example 1 is that in this comparative example, in the process of preparing the positive electrode, no activated carbon material is added, but only an active material such as lithium iron phosphate.
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
其余制备方法与参数与实施例1保持一致。The rest of the preparation methods and parameters are the same as those in Example 1.
测试标准：QCT741-2014车用超级电容器的标准进行测试。Test standard: QCT741-2014 standard for automotive supercapacitors.
表1为实施例1-10与对比例1所制得的锂离子电容器的电化学性能。Table 1 shows the electrochemical properties of the lithium ion capacitors prepared in Examples 1-10 and Comparative Example 1.
表1Table 1
Figure PCTCN2021085412-appb-000001
Figure PCTCN2021085412-appb-000001
从实施例1-4的数据结果可知，本发明所提供的锂离子电容器具有高倍率(5C容量是1C的96％以上)和优异的低温性能(-20℃是25℃的79％以上)。From the data results of Examples 1-4, it can be seen that the lithium ion capacitor provided by the present invention has high rate (5C capacity is more than 96% of 1C) and excellent low temperature performance (-20°C is more than 79% of 25°C).
从实施例1与实施例5和6的数据结果可知，无论是制备正极材料还是制备负极材料的过程的，所使用的原料的质量比超过本发明优选的质量比，其倍率和低温性能均会较低，原因为电极的导电性、粘结性变差。From the data results of Example 1 and Examples 5 and 6, it can be seen that in the process of preparing the positive electrode material or the negative electrode material, the mass ratio of the raw materials used exceeds the preferred mass ratio of the present invention, and the rate and low temperature performance will be reduced. The reason is that the conductivity and adhesiveness of the electrodes are deteriorated.
从实施例1与实施例7和8的数据结果可知，无论是正极面电阻较高还是负极面电阻较高，均会影响锂离子电容器的倍率性能和低温性能，使其性能降低。From the data results of Example 1 and Examples 7 and 8, it can be seen that whether the positive surface resistance is higher or the negative surface resistance is higher, it will affect the rate performance and low temperature performance of the lithium ion capacitor, and its performance will be reduced.
从实施例1与实施例9的数据结果可知，正极材料中的磷酸铁锂的D50过大会导致锂离子扩散速率降低，影响倍率性能和低温性能。From the data results of Example 1 and Example 9, it can be seen that the excessive D50 of lithium iron phosphate in the positive electrode material will lead to a decrease in the diffusion rate of lithium ions, which affects the rate performance and low temperature performance.
从实施例1与实施例10的数据结果可知，负极材料中的碳材料的晶面间距d002过小时会导致锂离子在负极中的嵌锂和脱出能力变差，从而影响倍率性能和低温性能。From the data results of Example 1 and Example 10, it can be seen that if the interplanar spacing d002 of the carbon material in the negative electrode material is too small, the lithium ion intercalation and extraction ability of the negative electrode will be deteriorated, thereby affecting the rate performance and low temperature performance.
从实施例1与对比例1的数据结果可知，仅将磷酸铁锂作为正极活性物质，不加入双电层材料时会导致倍率性能变差。It can be seen from the data results of Example 1 and Comparative Example 1 that only lithium iron phosphate is used as the positive electrode active material, and the rate performance is deteriorated when no electric double layer material is added.
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。The applicant declares that the above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should Changes or substitutions that can be easily conceived within the technical scope all fall within the protection scope and disclosure scope of the present invention.

Claims (10)

  1. 一种锂离子电容器，其特征在于，所述锂离子电容器包括正极、负极、隔膜和电解液；所述正极的材料包括磷酸铁锂、双电层材料、导电剂和粘结剂；所述负极的材料包括晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂。A lithium ion capacitor, characterized in that the lithium ion capacitor comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte; the material of the positive electrode comprises lithium iron phosphate, an electric double layer material, a conductive agent and a binder; the negative electrode The material includes carbon material with interplanar spacing d002 of at least 0.345nm, conductive agent and binder.
  2. 根据权利要求1所述的锂离子电容器，其特征在于，所述磷酸铁锂、双电层材料、导电剂和粘结剂的质量比为(45～90):(5～45):(3～10):(2～10)；The lithium ion capacitor according to claim 1, wherein the mass ratio of the lithium iron phosphate, the electric double layer material, the conductive agent and the binder is (45～90):(5～45):(3 ~10):(2~10);
    优选地，所述磷酸铁锂的D50为0.5～10μm；Preferably, the D50 of the lithium iron phosphate is 0.5-10 μm;
    优选地，所述双电层材料的比表面积为800～3600m 2/g； Preferably, the specific surface area of the electric double layer material is 800-3600 m 2 /g;
    优选地，所述双电层材料包括多孔碳材料；Preferably, the electric double layer material comprises a porous carbon material;
    优选地，所述磷酸铁锂和多孔碳材料的质量比为(1～18):1；Preferably, the mass ratio of the lithium iron phosphate to the porous carbon material is (1-18):1;
    优选的，所述多孔碳材料包括活性炭、碳纳米管、介孔碳、碳气凝胶、骨架炭或石墨烯中的任意一种或至少两种的组合；Preferably, the porous carbon material comprises any one or a combination of at least two of activated carbon, carbon nanotubes, mesoporous carbon, carbon aerogel, skeleton carbon or graphene;
    优选地，所述正极的材料中的导电剂包括炭黑、导电石墨、气相生长碳纤维、碳纳米管或石墨烯中的任意一种或至少两种的组合；Preferably, the conductive agent in the material of the positive electrode comprises any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene;
    优选地，所述正极的材料中的粘结剂包括聚偏氟乙烯、羧甲基纤维素钠、丁苯橡胶、聚丙烯酸、聚四氟乙烯、聚丙烯腈或聚丙烯酸酯中的任意一种或至少两种的组合。Preferably, the binder in the material of the positive electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
  3. 根据权利要求1或2所述的锂离子电容器，其特征在于，所述晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂的质量比为(80～98):(0.001～10):(2～10)；The lithium ion capacitor according to claim 1 or 2, characterized in that, the mass ratio of the carbon material with the interplanar spacing d002 of at least 0.345 nm, the conductive agent and the binder is (80～98):(0.001～ 10):(2～10);
    优选地，所述晶面间距d002至少为0.345nm的碳材料包括硬碳和/或软碳；Preferably, the carbon material with interplanar spacing d002 of at least 0.345 nm includes hard carbon and/or soft carbon;
    优选地，所述硬碳的D50为0.5～15μm；Preferably, the D50 of the hard carbon is 0.5-15 μm;
    优选地，所述硬碳的晶面间距d002大于或等于0.38nm；Preferably, the interplanar spacing d002 of the hard carbon is greater than or equal to 0.38 nm;
    优选地，所述软碳的D50为2～20μm；Preferably, the D50 of the soft carbon is 2-20 μm;
    优选地，所述软碳的晶面间距d002大于或等于0.345nm；Preferably, the interplanar spacing d002 of the soft carbon is greater than or equal to 0.345 nm;
    优选地，所述负极的材料中的导电剂包括炭黑、导电石墨、气相生长碳纤维、碳纳米管或石墨烯中的任意一种或至少两种的组合；Preferably, the conductive agent in the material of the negative electrode comprises any one or a combination of at least two of carbon black, conductive graphite, vapor-grown carbon fiber, carbon nanotube or graphene;
    优选地，所述负极的材料中的粘结剂包括聚偏氟乙烯、羧甲基纤维素钠、丁苯橡胶、聚丙烯酸、聚四氟乙烯、聚丙烯腈或聚丙烯酸酯中的任意一种或至少两种的组合。Preferably, the binder in the material of the negative electrode includes any one of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyacrylic acid, polytetrafluoroethylene, polyacrylonitrile or polyacrylate or a combination of at least two.
  4. 根据权利要求1-3任一项所述的锂离子电容器，其特征在于，所述隔膜包括纤维素隔膜、PET无纺布隔膜、芳纶隔膜、PET无纺布陶瓷填充隔膜、PE陶瓷涂覆隔膜或PP陶瓷涂覆隔膜中的任意一种或至少两种的组合；The lithium ion capacitor according to any one of claims 1-3, wherein the separator comprises a cellulose separator, a PET non-woven separator, an aramid separator, a PET non-woven ceramic-filled separator, and a PE ceramic coating Any one or a combination of at least two of the diaphragm or the PP ceramic coated diaphragm;
    优选地，所述隔膜的孔隙率大于或等于45％；Preferably, the porosity of the membrane is greater than or equal to 45%;
    优选地，所述隔膜的透气度小于或等于200s/100mL。Preferably, the air permeability of the membrane is less than or equal to 200s/100mL.
  5. 根据权利要求1-4任一项所述的锂离子电容器，其特征在于，所述电解液包括六氟磷酸锂、溶剂和添加剂；The lithium ion capacitor according to any one of claims 1-4, wherein the electrolyte comprises lithium hexafluorophosphate, a solvent and an additive;
    优选地，所述六氟磷酸锂的摩尔浓度为0.8～1.5mol/L；Preferably, the molar concentration of the lithium hexafluorophosphate is 0.8-1.5 mol/L;
    优选地，所述溶剂包括碳酸乙烯酯、碳酸甲乙酯、乙酸乙酯和丙酸乙酯；Preferably, the solvent includes ethylene carbonate, ethyl methyl carbonate, ethyl acetate and ethyl propionate;
    以溶剂和添加剂的质量总和为100％计：Based on the sum of the mass of solvent and additives as 100%:
    优选地，所述碳酸乙烯酯在所述电解液中的质量分数为7～13wt％；Preferably, the mass fraction of the ethylene carbonate in the electrolyte is 7-13 wt%;
    优选地，所述碳酸甲乙酯在所述电解液中的质量分数为7～13wt％；Preferably, the mass fraction of the ethyl methyl carbonate in the electrolyte is 7-13 wt%;
    优选地，所述乙酸乙酯在所述电解液中的质量分数为70～80wt％；Preferably, the mass fraction of the ethyl acetate in the electrolyte is 70-80 wt%;
    优选地，所述丙酸乙酯在所述电解液中的质量分数为1～5wt％；Preferably, the mass fraction of the ethyl propionate in the electrolyte is 1-5wt%;
    优选地，所述添加剂包括碳酸亚乙烯酯、氟代碳酸乙烯酯和硫酸乙烯酯；Preferably, the additives include vinylene carbonate, fluoroethylene carbonate and vinyl sulfate;
    优选地，所述碳酸亚乙烯酯在所述电解液中的质量分数为1～2wt％；Preferably, the mass fraction of the vinylene carbonate in the electrolyte is 1-2 wt%;
    优选地，所述氟代碳酸乙烯酯在所述电解液中的质量分数为0.5～1.5wt％；Preferably, the mass fraction of the fluoroethylene carbonate in the electrolyte is 0.5-1.5 wt %;
    优选地，所述硫酸乙烯酯在所述电解液中的质量分数为0.5～1.5wt％；Preferably, the mass fraction of the vinyl sulfate in the electrolyte is 0.5-1.5 wt%;
    优选地，所述电解液的室温离子电导率大于或等于12mS/cm。Preferably, the room temperature ionic conductivity of the electrolyte is greater than or equal to 12 mS/cm.
  6. 根据权利要求1-5任一项所述的锂离子电容器的制备方法，其特征在于，所述制备方法包括：The preparation method of a lithium ion capacitor according to any one of claims 1-5, wherein the preparation method comprises:
    将正极、负极与隔膜叠加，形成叠加电芯；将所述叠加电芯注入电解液，再经过抽气、封口，得到所述锂离子电容器；superimposing the positive electrode, the negative electrode and the diaphragm to form a superimposed cell; injecting the superimposed cell into the electrolyte, and then exhausting and sealing to obtain the lithium ion capacitor;
    所述正极的制备方法包括：将磷酸铁锂、双电层材料、导电剂和粘结剂混合制成浆料，将所述浆料涂覆在正极集流体上，干燥，辊压，得到所述正极；The preparation method of the positive electrode includes: mixing lithium iron phosphate, an electric double layer material, a conductive agent and a binder to prepare a slurry, coating the slurry on the positive electrode current collector, drying and rolling to obtain the obtained slurry. the positive electrode;
    所述负极的制备方法包括：将晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂混合制成浆料，涂覆在负极集流体上，干燥，辊压得到所述负极。The preparation method of the negative electrode includes: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder to prepare a slurry, coating the negative electrode current collector, drying, and rolling to obtain the negative electrode.
  7. 根据权利要求6所述的锂离子电容器的制备方法，其特征在于，对所述正极和负极分别进行裁切后得到正极片和负极片，再与隔膜进行叠加；The method for preparing a lithium ion capacitor according to claim 6, wherein the positive electrode and the negative electrode are respectively cut to obtain a positive electrode sheet and a negative electrode sheet, which are then stacked with the separator;
    优选地，所述叠加操作的仪器为自动叠片机；Preferably, the instrument for the stacking operation is an automatic stacking machine;
    优选地，所述叠加电芯两侧各放置一片金属锂片；Preferably, a metal lithium sheet is placed on each side of the superimposed battery cell;
    优选地，所述注入电解液操作前对叠加电芯进行高温干燥，超声焊接和顶侧封操作。Preferably, high temperature drying, ultrasonic welding and top and side sealing operations are performed on the superposed cells before the operation of injecting the electrolyte.
  8. 根据权利要求6或7所述的锂离子电容器的制备方法，其特征在于，所述辊压后的正极的压实密度为1.3～2.2g/cm 3； The method for preparing a lithium ion capacitor according to claim 6 or 7, wherein the compaction density of the positive electrode after rolling is 1.3-2.2 g/cm 3 ;
    优选地，所述正极集流体的厚度为15～30μm；Preferably, the thickness of the positive electrode current collector is 15-30 μm;
    优选地，所述正极集流体包括表面涂有导电涂层的铝箔、铝网或经过表面处理的铝箔中的任意一种或至少两种的组合；Preferably, the positive electrode current collector comprises any one or a combination of at least two of aluminum foil, aluminum mesh or surface-treated aluminum foil coated with a conductive coating on the surface;
    优选地，所述正极的正极面电阻小于或等于10Ω·cm 2； Preferably, the positive surface resistance of the positive electrode is less than or equal to 10Ω·cm 2 ;
    优选地，所述辊压后的负极的压实密度为0.8～1.4g/cm3；Preferably, the compaction density of the negative electrode after rolling is 0.8-1.4 g/cm3;
    优选地，所述负极集流体的厚度为10～25μm；Preferably, the thickness of the negative electrode current collector is 10-25 μm;
    优选地，所述负极集流体包括表面涂有导电涂层的铜箔、铜网或经过表面处理的铜箔中的任意一种或至少两种的组合；Preferably, the negative electrode current collector comprises any one or a combination of at least two of copper foil, copper mesh or surface-treated copper foil coated with a conductive coating on the surface;
    优选地，所述负极的负极面电阻小于或等于3Ω·cm 2； Preferably, the negative surface resistance of the negative electrode is less than or equal to 3Ω·cm 2 ;
    优选地，所述负极比容量和正极比容量的比值N/P比为2～3.5。Preferably, the ratio N/P ratio of the specific capacity of the negative electrode and the specific capacity of the positive electrode is 2˜3.5.
  9. 根据权利要求6-8任一项所述的锂离子电容器的制备方法，其特征在于，所述制备方法包括：The preparation method of a lithium ion capacitor according to any one of claims 6-8, wherein the preparation method comprises:
    将正极、负极分别裁切成正极片和负极片，与隔膜在自动叠片机上叠成电芯，在电芯两侧各放置一片金属锂片，通过高温干燥，超声焊接、顶侧封、注入所述电解液、抽气、封口，得到所述锂离子电容器；Cut the positive electrode and the negative electrode into positive and negative electrode sheets respectively, stack them with the separator on an automatic stacking machine to form a battery cell, place a metal lithium sheet on each side of the battery cell, dry at high temperature, ultrasonic welding, top side sealing, injection The electrolyte, pumping, and sealing to obtain the lithium ion capacitor;
    所述正极的制备方法包括：将磷酸铁锂、多孔炭、导电剂和粘结剂按照(45～90):(5～45):(3～10):(2～10)的质量比混合制成浆料，涂覆在厚度为15～30μm的正极集流体上，干燥，辊压，压实密度为1.3～2.2g/cm 3，得到所述正极，所述正极的正极面电阻小于或等于10 Ω·cm 2； The preparation method of the positive electrode comprises: mixing lithium iron phosphate, porous carbon, conductive agent and binder according to the mass ratio of (45-90):(5-45):(3-10):(2-10) Slurry is made, coated on a positive electrode current collector with a thickness of 15-30 μm, dried, rolled, and compacted at a density of 1.3-2.2 g/cm 3 to obtain the positive electrode whose positive surface resistance of the positive electrode is less than or is equal to 10 Ω·cm 2 ;
    所述负极的制备方法包括：将晶面间距d002至少为0.345nm的碳材料、导电剂和粘结剂以(80～98):(0～10):(2～10)的质量比混合制成浆料，涂覆在厚度为10～25μm的负极集流体上，干燥，辊压得到所述负极，负极的负极面电阻小于或等于3Ω·cm 2。 The preparation method of the negative electrode comprises: mixing a carbon material with a crystal plane spacing d002 of at least 0.345 nm, a conductive agent and a binder in a mass ratio of (80-98):(0-10):(2-10) Slurry is formed, coated on a negative electrode current collector with a thickness of 10-25 μm, dried, and rolled to obtain the negative electrode, and the negative electrode surface resistance of the negative electrode is less than or equal to 3Ω·cm 2 .
  10. 如权利要求1-5任一项所述的锂离子电容器的用途，其特征在于，所述用途包括将所述的锂离子电容器用作储能器件。The use of a lithium ion capacitor according to any one of claims 1 to 5, characterized in that, the use comprises using the lithium ion capacitor as an energy storage device.
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