CN110182807A - A kind of zirconium doped porous carbon material and the preparation method for preparing lithium-ion capacitor battery anode composite - Google Patents
A kind of zirconium doped porous carbon material and the preparation method for preparing lithium-ion capacitor battery anode composite Download PDFInfo
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- CN110182807A CN110182807A CN201910329068.7A CN201910329068A CN110182807A CN 110182807 A CN110182807 A CN 110182807A CN 201910329068 A CN201910329068 A CN 201910329068A CN 110182807 A CN110182807 A CN 110182807A
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/48—Carbon black
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- 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
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to lithium ion batteries and supercapacitor technologies field, and in particular to a kind of zirconium doped porous carbon material and the preparation method for preparing lithium-ion capacitor battery anode composite.Zirconium doped porous carbon material of the invention passes through first porous carbon materials surface uniformly coats with coprecipitation one layer of 4 particle of nanometer Zr (OH), the method for heating and thermal insulation is made in protective atmosphere；The preparation method of lithium-ion capacitor battery anode composite is prepared in the present invention using above-mentioned zirconium doped porous carbon material, comprising the following steps: (1) lithium electricity positive electrode, conductive agent and zirconium doped porous carbon material are uniformly mixed as mixed active material；(2) mixed active material is coated on collector to get anode composite.Zirconium doped porous carbon material is applied to prepare lithium-ion capacitor battery anode composite by the present invention, can be improved the chemical property and security performance of capacitor batteries.
Description
Technical field
The present invention relates to lithium ion batteries and supercapacitor technologies field, and in particular to a kind of zirconium doped porous carbon material
And the preparation method of super capacitor lithium ion anode composite is prepared using the zirconium doped porous carbon material.
Background technique
Lithium ion battery is that a kind of energy density is big, and average output voltage is high, and self discharge is small and without noxious material
Green secondary cell.It has passed through nearly vicennial development, the energy density of lithium ion battery can reach 100Wh/kg and arrive
150Wh/kg, operating voltage maximum is up to 4V.Super capacitor is based on electric double layer energy storage principle and the higher oxidation of invertibity
The energy storage device for restoring pseudo-capacitance principle, with power density is high, the charge and discharge time is short, has extended cycle life, operating temperature range
The advantages that wide, while also there is the relatively low disadvantage of energy density.Lithium ion battery and super capacitor in specific energy and compare function
Difference in rate determines the difference of the two charge-discharge velocity, and in actual application, due to super capacitor and lithium-ion electric
Pond has the advantages that respectively to protrude and limitation, the two combine parallel or tandem capacitor batteries using more
The blank of this part is mended.It is in the prior art usually that a certain amount of porous carbon is mixed in the positive electrode of lithium ion battery
Material, forms the composite positive pole of lithium-ion capacitor battery, porous carbon materials include active carbon, mesoporous carbon, carbon nanotube, graphite
Alkene etc..However due to being influenced in preparation process by technique and cost, the composite effect of composite positive pole is unsatisfactory, nothing
Method reaches evenly dispersed and Nano grade mixing.And due to the normal oxygen-containing functional group rich in porous carbon materials surface,
To improve the infiltration of electrode in the electrolytic solution, it is anti-that some poorly reversible pairs can occur in charge and discharge process for oxygen-containing functional group
It answers, but to influence the performances such as cycle life, self discharge, the AC impedance of porous carbon materials.
Cobalt acid lithium of the development course of lithium electricity positive electrode from layer structure, the LiMn2O4 of spinel structure, olivine knot
The ferrophosphorus acid lithium of structure is to ternary material lithium nickel cobalt manganese.Lithium cobaltate cathode material is that the main of lithium electricity in current conditional electronic product makes
With material, it is mainly based upon the advantages such as its capacity is big, voltage range is big.LiMn2O4 due to its low price, stabilization, conduct electricity very well
Advantage is widely applied in fields such as electric bicycle, electric cars, but there is also its capacity fade problems.Recently as using
The public transport of clean energy resource is greatly developed, the lithium iron phosphate positive material of olivine structural and more technology frontier development
Ternary material lithium nickel cobalt manganese is widely applied to electric car and extensive energy storage device.
Plasma spraying method is using the plasma-arc by DC powered as heat source, by ceramics, alloy, metal
Equal materials are heated to melting or semi-molten state, and form adhesion-tight to spray at a high speed by pretreated workpiece surface
The method of superficial layer.This method is carried out using plasma arc, and ion arc is compression arc, compared with free electric arc, arc
Column is thin, and current density is big, and gas ionization degree is high, therefore has the features such as temperature is high, and energy is concentrated, and arc stbility is good.
Summary of the invention
The purpose of the present invention is in view of the above technical problems, proposing a kind of zirconium doped porous carbon material, which is adulterated more
Hole carbon material is applied to prepare lithium-ion capacitor battery anode composite, to improve chemical property and the safety of capacitor batteries
Energy.
In order to achieve the above object of the invention, the invention adopts the following technical scheme:
A kind of zirconium doped porous carbon material, which is characterized in that the zirconium doped porous carbon material passes through first in porous carbon
Material surface uniformly coats one layer of nanometer Zr (OH) with coprecipitation4Particle, the method for heating and thermal insulation is made in protective atmosphere.
Preferably, the porous carbon materials include active carbon, mesoporous carbon, carbon aerogels, carbon fiber, carbon nanotube, charcoal
One of black, hard charcoal or graphene are a variety of.
Preferably, the partial size of the active carbon and mesoporous carbon is 1-20 μm, the carbon airsetting in the porous carbon materials
The partial size of glue is 5-20nm, and the diameter of the carbon fiber is 5-20 μm, and the diameter of the carbon nanotube is 5-20nm, the carbon black
Partial size be 20-80nm, the graphene with a thickness of 3-30nm.
Preferably, described uniformly coat one layer of nanometer Zr (OH) with coprecipitation4The process of particle are as follows: by porous carbon
Material is added to Zr (NO3)4Suspension is made in solution, then addition NaOH solution adjusting pH value to alkalinity, removes supernatant after standing
Liquid, with washes of absolute alcohol, vacuum drying obtains a nanometer Zr (OH)4The porous carbon materials of package.
Preferably, the porous carbon materials first successively carry out ultrasound clearly with water and dehydrated alcohol before suspension is made
It washes, to remove wherein impurity, and increases porous carbon materials and Zr (NO3)4The affinity of solution.
Preferably, Zr (the NO3)4The concentration of solution is 0.2mol/L-0.3mol/L.
Preferably, the porous carbon materials and Zr (NO3)4Suspension is made according to the ratio of 3.0g/L-4.0g/L,
Preferably, the concentration of the NaOH solution is 0.3mol/L-0.5mol/L.
Preferably, the addition NaOH solution adjusts pH value to 7.5-8.0,
Preferably, the time of the standing is 22-24h.
The present invention passes through control Zr (NO3)4The molar concentration of solution, the concentration of NaOH solution and porous carbon materials and Zr
(NO3)4Ratio, control generate nanometer Zr (OH)4And the size of nanometer Zr particle, finally by the size control of nanometer Zr particle
System is within the scope of 10-30nm.
Preferably, the process of the heating and thermal insulation is, under inert gas atmosphere protection, with the heating of 8-10 DEG C/min
Speed is heated to 70-100 DEG C, keeps the temperature 30-50min, then be heated to 420-450 DEG C with the heating speed of 13-20 DEG C/min, heat preservation
30-60min。
The present invention is guaranteed Zr (OH) by heating speed, temperature and soaking time during control heating and thermal insulation4?
ZrO is generated with stable speed dehydration when 70-100 DEG C2, crystal transfer is completed at a temperature of 420-450 DEG C, forms structure
Close nano zircite particle.
Another object of the present invention, which is provided, prepares lithium-ion capacitor battery with again using above-mentioned zirconium doped porous carbon material
Close the preparation method of anode, comprising the following steps:
(1) lithium electricity positive electrode, conductive agent and zirconium doped porous carbon material are uniformly mixed as mixed active material；
(2) mixed active material is coated on collector to get anode composite.
The often surface oxygen-containing functional group rich in of the porous carbon materials used in capacitor batteries, is existed with improving electrode
Some poorly reversible side reactions can occur in charge and discharge process for the infiltration in electrolyte, oxygen-containing functional group, but to influence
The performances such as cycle life, self discharge, the AC impedance of porous carbon materials.The present invention mixes porous carbon materials using zr element
Miscellaneous, after overdoping, zr element forms tiny nano zircite particle on porous carbon materials surface, can reduce porous carbon
Material and electrolyte directly contact, and reduce the generation of side reaction, and there are tiny holes between nano particle, can improve porous carbon
The wellability of material shortens the transmission path of negative ions in electrolyte, can also increase the contact area of electrode and electrolyte, be anti-
More active sites should be provided, provide more memory spaces for lithium ion；Hole and carbon between Zirconium oxide nano grain
The porous structure of material itself can effectively buffer zirconium while promoting inside electrolyte permeability to zirconium doped porous carbon material
Negative ions are moved to electrode surface and are born during electrode surface release doped porous carbon material in the electrolytic solution
Impact, to be conducive to improve the performances such as electrochemical cycle stability and the multiplying power of capacitor batteries.The zr element part of doping with
Carbon generates zirconium carbide, and high-valence state zirconium therein can generate more excess electron, improves electronic conductivity.In addition, nano zircite
It can be improved the high temperature resistance and intensity of combination electrode.
The present invention controls the active material of positive electrode within the scope of Nano grade, can effectively ensure that active material
The performance of energy, to improve the performance of capacitor batteries.
Preferably, the weight percent of the lithium electricity positive electrode, conductive agent and porous carbon materials is respectively 15-
20%, 5-20% and 60-80%.
Preferably, the lithium electricity positive electrode includes LiCoO2、LiMn2O4、LiMnO2、LiNiO2、LiFePO4、
LiMnPO4、LiNi0.8Co0.2O2Or LiNi1/3Co1/3Mn1/3O2One of or it is a variety of.
Preferably, the partial size of the lithium electricity positive electrode is 10-100nm.
Preferably, the conductive agent is one of conductive black, graphene or carbon nanotube or a variety of.
Preferably, in the conductive agent, the partial size of the conductive black is 20-80nm, the graphene with a thickness of
3-30nm, the diameter of the carbon nanotube are 5-20nm.
Preferably, it is described by mixed active material be coated on collector before also have pass through plating on a current collector
Method formed tin transition zone the step of.
The coating that plasma spraying technology is formed is since the material difference of coating and base is larger, and coating is in cooling and solidification
What is generated in the process is contracted in coating and base's contact interface generation stress, and this stress often generates drawing in corner angle and edge and answers
Power, and crackle can be caused convenient, crackle is under certain condition, it may occur that extension ultimately causes disbonding.This hair by
Collector life presets the preferable tin transition zone of one layer of toughness, what crackle caused by can reduce because of tensile stress between interface generated
Probability, thus a possibility that improving coating quality, reducing disbonding.It is often generated using the coating that thermal processing method is formed
Stress, the present invention can be avoided the generation of stress in transition zone using the cold working mode of plating, to improve coating as far as possible
The quality of layer.
Preferably, the collector is utter misery aluminium foil, aluminium foil, aluminium foil with holes, copper foil or copper foil with holes.
Preferably, the collector with a thickness of 7-23 μm.
Preferably, described be coated to mixed active material on collector to be applied using plasma spraying technology
It covers, then carries out heat treatment and cooling drying.
In the preparation of existing capacitor batteries, the positive electrode of porous carbon materials and lithium ion battery, which is unable to reach, uniformly to be divided
Scattered and Nano grade mixing, therefore composite effect is not ideal enough, it is difficult to so that capacitor batteries is reached preferable performance.The present invention
The active material of capacitor batteries Nano grade is quickly ejected on collector using plasma spraying technology, so as to obtain
The lithium electricity positive electrode and porous carbon composite being uniformly mixed on nano-scale, with the capacitor batteries being had excellent performance.
Preferably, the plasma spraying technology include low-temp low-pressure plasma technology, high-temperature low-pressure plasma technology,
The steady plasma technology of vacuum plasma technology, water or the steady plasma technology of gas.
Preferably, it is described by mixed active material be coated to the jet velocity on collector be 4-6m/min, the painting
Cover with a thickness of 50-120 μm.
Preferably, described be applied to dual coating.
Preferably, the heat treatment is to be coated to mixed active material on collector using plasma spraying technology
Afterwards, it is then cooled to 200-400 DEG C of temperature in 600-700 DEG C of temperature 3-8min immediately and continues to keep the temperature 3-5min.
The present invention is heat-treated by two-part, can effectively avoid coating layer of active substance after routinely coating because being quickly cooled down
With solidification and generate more stress, and make coating and transition zone and base that there is better amalgamation, to reduce coat
A possibility that peeling.
Compared with prior art, the present invention beneficial effect is: the present invention passes through to porous in capacitor batteries positive electrode
Carbon material is modified, and is reduced the generation of porous carbon materials Yu electrolyte side reaction, is improved porous carbon materials and electrolyte
Wellability, to improve the electric property of anode composite；It solves in capacitor batteries and receives by plasma spraying method simultaneously
Meter level lithium electricity positive electrode and capacitance cathode material are difficult to evenly dispersed problem.
Specific embodiment
Below by specific embodiment the technical scheme of the present invention will be further described explanation.
If raw material employed in the embodiment of the present invention is raw material commonly used in the art without specified otherwise, implement
Method employed in example, is the conventional method of this field.
Embodiment 1
The present embodiment is the preparation embodiment of zirconium doped porous carbon material, specifically:
Active carbon (South Korea PCT, particle size range are 1-20 μm, and average grain diameter is 5.5 μm) is successively used into water and dehydrated alcohol
It is cleaned by ultrasonic, the Zr (NO of 0.2mol/L is added according to the ratio of 3.5g/L3)4Suspension is made in solution, is then added
The NaOH solution of 0.4mol/L adjusts pH value to 8.0, and standing removes supernatant afterwards for 24 hours, with washes of absolute alcohol, vacuum drying,
Obtain a nanometer Zr (OH)4The porous carbon materials of package；
Then 87 DEG C are heated to the heating speed of 9 DEG C/min in an ar atmosphere, keep the temperature 40min, then with 16 DEG C/min's
Heating speed is heated to 430 DEG C, keeps the temperature 45min to get zirconium doped porous carbon material.
Embodiment 2
The present embodiment is the preparation embodiment of zirconium doped porous carbon material, specifically:
Active carbon (South Korea PCT, particle size range are 1-20 μm, and average grain diameter is 5.5 μm) is successively used into water and dehydrated alcohol
It is cleaned by ultrasonic, the Zr (NO of 0.2mol/L is added according to the ratio of 3.0g/L3)4Suspension is made in solution, is then added
The NaOH solution of 0.3mol/L adjusts pH value to 7.5, removes supernatant after standing 22h, with washes of absolute alcohol, vacuum drying,
Obtain a nanometer Zr (OH)4The porous carbon materials of package；
Then 70 DEG C are heated to the heating speed of 8 DEG C/min in an ar atmosphere, keep the temperature 50min, then with 13 DEG C/min's
Heating speed is heated to 420 DEG C, keeps the temperature 60min to get zirconium doped porous carbon material.
Embodiment 3
The present embodiment is the preparation embodiment of zirconium doped porous carbon material, specifically:
Active carbon (South Korea PCT, particle size range are 1-10 μm, and average grain diameter is 3.3 μm) is successively used into water and dehydrated alcohol
It is cleaned by ultrasonic, the Zr (NO of 0.3mol/L is added according to the ratio of 4.0g/L3)4Suspension is made in solution, is then added
The NaOH solution of 0.5mol/L adjusts pH value to 8.0, and standing removes supernatant afterwards for 24 hours, with washes of absolute alcohol, vacuum drying,
Obtain a nanometer Zr (OH)4The porous carbon materials of package；
Then 100 DEG C are heated to the heating speed of 10 DEG C/min in an ar atmosphere, keep the temperature 20min, then with 20 DEG C/min
Heating speed be heated to 450 DEG C, keep the temperature 30min to get zirconium doped porous carbon material.
Embodiment 4
The present embodiment is the preparation embodiment of lithium-ion capacitor battery anode composite, comprising the following steps:
(1) prepare raw material: by weight percentage, 20%LiFePO4(garden Tai Suchang), 10% conductive black
(TIMCAL) zirconium doped porous carbon material obtained, LiFePO and in 70% embodiment 14Particle size range be 30-70nm, put down
Equal partial size is 46nm, and the particle size range of conductive black is 20-80nm, average grain diameter 50nm.
(3) the tin transition zone of one layer of 3 μ m-thick is formed by electric plating method in the aluminum foil current collector of 20 μ m-thicks.
(4) by LiFePO4, conductive black and zirconium dopped activated carbon be uniformly mixed as mixed active material, by mixed active
Substance is added in the powder feeder of plasma jets, and on a current collector using the coating of plasma spraying technology, jet velocity is
Then 5m/min is cooled to 370 DEG C of temperature and continues to keep the temperature 5min in 660 DEG C of temperature 7min immediately after coating, then cooling
It is drying to obtain anode composite, is applied to dual coating, single side coating thickness is 90 μm.
Anode composite density obtained is 0.94g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece is it is found that zirconium dopped activated carbon in anode composite pole piece, conductive black and lithium iron phosphate particles are uniformly mixed, LiFePO4 surface
Uniform coated with conductive carbon black and zirconium dopped activated carbon mixture.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 3.65V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 37.8Wh/kg, and specific power is
3920W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 92.5%.
Embodiment 5
The present embodiment is the preparation embodiment of lithium-ion capacitor battery anode composite, comprising the following steps:
(1) prepare raw material: by weight percentage, 17%LiMnPO4(Ningbo material institute), 10% conductive black
(TIMCAL), zirconium doped porous carbon material obtained in 1% graphene (taking in the fresh in Yancheng) and 72% embodiment 1, LiMnPO4Grain
Diameter range is 20-80nm, and average grain diameter 50nm, the particle size range of conductive black is 20-80nm, average grain diameter 43nm, stone
The thickness range of black alkene is 3-30nm, average thickness 15nm.
(3) the tin transition zone of one layer of 4 μ m-thick is formed by electric plating method in the aluminum foil current collector of 20 μ m-thicks.
(4) by LiMnPO4, conductive black and zirconium dopped activated carbon be uniformly mixed as mixed active material, by mixed active
Substance is added in the powder feeder of plasma jets, and on a current collector using the coating of plasma spraying technology, jet velocity is
Then 5m/min is cooled to 330 DEG C of temperature and continues to keep the temperature 5min, then cool down in 600 DEG C of temperature 8min immediately after coating
It is drying to obtain anode composite, is applied to dual coating, single side coating thickness is 95 μm.
Anode composite density obtained is 0.87g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece it is found that zirconium dopped activated carbon, conductive black, graphene and lithium manganese phosphate particle are uniformly mixed in anode composite pole piece, mix by zirconium
Miscellaneous active carbon, conductive black, lithium manganese phosphate are evenly distributed on the conductive structure of single-layer graphene, and lithium manganese phosphate surface is coated with
Conductive black.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 4.3V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 54.5Wh/kg, and specific power is
4530W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 94.6%.
Embodiment 6
The present embodiment is the preparation embodiment of lithium-ion capacitor battery anode composite, comprising the following steps:
(1) prepare raw material: by weight percentage, 20%LiNi1/3Co1/3Mn1/3O2(Shenzhen Bei Terui) (Ningbo material
Expect institute), (zirconium doping is active for zirconium doped porous carbon material obtained in 15% conductive black (TIMCAL) and 65% embodiment 1
Charcoal), LiNi1/3Co1/3Mn1/3O2Particle size range be 37-80nm, the particle size range of average grain diameter 52nm, conductive black is
20-80nm, average grain diameter 43nm.
(2) the tin transition zone of one layer of 5 μ m-thick is formed by electric plating method in the aluminum foil current collector of 20 μ m-thicks.
(3) by LiNi1/3Co1/3Mn1/3O2, conductive black and zirconium dopped activated carbon be uniformly mixed as mixed active material, will
Mixed active material is added in the powder feeder of plasma jets, on a current collector using the coating of plasma spraying technology, spray
Firing rate degree is 5m/min, is then cooled to 400 DEG C of temperature in 700 DEG C of temperature 5min immediately after coating and continues to keep the temperature 3min,
Then cooling is drying to obtain anode composite, is applied to dual coating, and single side coating thickness is 90 μm.
Anode composite density obtained is 1.01g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece is it is found that zirconium dopped activated carbon in anode composite pole piece, conductive black and ternary cobalt nickel manganese particle are uniformly mixed, ternary cobalt nickel manganese
Surface is coated with conductive black.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 4.2V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 56.3Wh/kg, and specific power is
4620W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 92.3%.
Comparative example 1
Active carbon is not modified, i.e., does not carry out zirconium doping, other are same as Example 4.
Anode composite density obtained is 0.93g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece it is found that active carbon, conductive black and lithium iron phosphate particles are uniformly mixed in anode composite pole piece, uniformly wrap by LiFePO4 surface
Cover conductive black and Mixture of Activated Carbon.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 3.65V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 35.9Wh/kg, and specific power is
3830W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 92.0%.
Comparative example 2
Tin transition zone is not preset in aluminum foil current collector, other are same as Example 4.
Anode composite density obtained is 0.93g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece it is found that active carbon, conductive black and lithium iron phosphate particles are uniformly mixed in anode composite pole piece, uniformly wrap by LiFePO4 surface
Cover conductive black and Mixture of Activated Carbon.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 3.65V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 37.5Wh/kg, and specific power is
3900W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 92.3%.
Comparative example 3
The coating of mixed active material on a current collector is carried out using usual manner, other are same as Example 4.
Anode composite density obtained is 0.94g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece it is found that active carbon, conductive black and lithium iron phosphate particles are uniformly mixed in anode composite pole piece, uniformly wrap by LiFePO4 surface
Cover conductive black and Mixture of Activated Carbon.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 3.65V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 36.1Wh/kg, and specific power is
3820W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 91.2%.
Comparative example 4
It is not heat-treated after mixed active material is coated on a current collector using plasma spraying technology, other and reality
It is identical to apply example 4.
Anode composite density obtained is 0.93g/cm3, anode composite obtained is subjected to SEM scanning, by SEM scanning figure
Piece it is found that active carbon, conductive black and lithium iron phosphate particles are uniformly mixed in anode composite pole piece, uniformly wrap by LiFePO4 surface
Cover conductive black and Mixture of Activated Carbon.
Anode composite obtained and graphite cathode are assembled, capacitor batteries are made, is carried out after 0.02C is melted into charge and discharge
Performance test charges to 3.65V with 1C, and 1C is discharged to 2.0V, and the specific energy of capacitor batteries is 37.3Wh/kg, and specific power is
3910W/kg, after 1C charge and discharge cycles 15000 times, capacity is maintained at 91.7%.
It is more that above-described embodiment 4, embodiment 5, embodiment 6 can also use the zirconium prepared in embodiment 2 or embodiment 3 to adulterate
Hole carbon material, the zirconium doped porous carbon material in above-described embodiment can also use active carbon, mesoporous carbon, carbon aerogels, carbon fiber
One of dimension, carbon nanotube, carbon black, hard charcoal or graphene or it is a variety of prepared for raw material, lithium electricity positive electrode can also be
LiCoO2、LiMn2O4、LiMnO2、LiNiO2Or LiNi0.8Co0.2O2, effect and the embodiment of the present application are close.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (9)
1. a kind of zirconium doped porous carbon material, which is characterized in that the zirconium doped porous carbon material passes through first in porous carbon materials
Surface uniformly coats one layer of nanometer Zr (OH) with coprecipitation4Particle, the method for heating and thermal insulation is made in protective atmosphere.
2. zirconium doped porous carbon material according to claim 1, which is characterized in that the process of the heating and thermal insulation is,
Under inert gas atmosphere protection, it is heated to 70-100 DEG C with the heating speed of 8-10 DEG C/min, keeps the temperature 30-50min, then with 13-
The heating speed of 20 DEG C/min is heated to 420-450 DEG C, keeps the temperature 30-60min.
3. a kind of lithium-ion capacitor battery anode composite preparation method, which comprises the following steps:
(1) zirconium doped porous carbon material described in lithium electricity positive electrode, conductive agent and claims 1 or 2 is uniformly mixed and is
Mixed active material；
(2) mixed active material is coated on collector to get anode composite.
4. the preparation method of lithium-ion capacitor battery anode composite according to claim 2, which is characterized in that the lithium
The partial size of electric positive electrode, conductive agent and modified porous carbon material is 10-100nm.
5. the preparation method of lithium-ion capacitor battery anode composite according to claim 2, which is characterized in that the lithium
The weight percent of electric positive electrode, conductive agent and porous carbon materials is respectively 15-20%, 5-20% and 60-80%.
6. the preparation method of lithium-ion capacitor battery anode composite according to claim 4 or 5, which is characterized in that institute
It states and mixed active material is coated on collector to be coated using plasma spraying technology, then carry out heat treatment and cold
But it dries.
7. the preparation method of lithium-ion capacitor battery anode composite according to claim 6, which is characterized in that described to incite somebody to action
Mixed active material also has the step for forming tin transition zone by electric plating method on a current collector before being coated on collector
Suddenly.
8. the preparation method of lithium-ion capacitor battery anode composite according to claim 6, which is characterized in that described to incite somebody to action
Mixed active material be coated to the jet velocity on collector be 4-6m/min, the coating with a thickness of 50-100 μm.
9. the preparation method of lithium-ion capacitor battery anode composite according to claim 1, which is characterized in that the heat
Processing is after being coated to mixed active material on collector using plasma spraying technology, immediately in 600-700 DEG C of temperature
3-8min is kept the temperature, 200-400 DEG C of temperature is then cooled to and continues to keep the temperature 3-5min.
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