WO2022088610A1 - Condensateur au lithium-ion, son procédé de fabrication et ses utilisations - Google Patents

Condensateur au lithium-ion, son procédé de fabrication et ses utilisations 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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English (en)
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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

Condensateur au lithium-ion, son procédé de fabrication et ses utilisations. Le condensateur au lithium-ion comprend une électrode positive, une électrode négative, un séparateur et une solution électrolytique. Les matériaux de l'électrode positive comprennent du phosphate de fer-lithium, un matériau électrique à double couche, un agent électroconducteur et un agent adhésif. Les matériaux de l'électrode négative comprennent un matériau carboné dont l'espacement interplan d002 est d'au moins 0,345 nm, un agent électroconducteur et un agent adhésif. À l'aide de substances actives d'électrodes positive et négative préférées ayant des paramètres appropriés, le mélange et le dosage des matériaux sont optimisés, la résistance interne d'un collecteur de courant est réduite, le séparateur présentant une porosité élevée et une faible perméabilité à l'air est préféré, la conductibilité électrique de la solution électrolytique à température ambiante et à basses températures est augmentée, la densité de compactage et la résistance de feuille sont régulées avec précision, la conductibilité électrique de languettes d'électrode et la mouillabilité de la solution électrolytique sont augmentées, et la polarisation est réduite, ce qui permet d'augmenter les performances de vitesse et les performances à basse-température du condensateur au lithium-ion à l'aide de phosphate de fer-lithium.
PCT/CN2021/085412 2020-10-29 2021-04-02 Condensateur au lithium-ion, son procédé de fabrication et ses utilisations WO2022088610A1 (fr)

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CN114566393A (zh) * 2022-03-23 2022-05-31 上海奥威科技开发有限公司 一种用于锂离子电容器的复合正极材料及其应用
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