CN102637879A - Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material - Google Patents
Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material Download PDFInfo
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Abstract
The invention relates to a micro-nano-structure anode material for a Li-air battery and a preparation method of the micro-nano-structure anode material. The preparation method comprises the following steps of: preparation of hollow composite precursor fibers through electrostatic spinning by blending a metal nitride catalyst precursor with a high-carbon polymer in an organic solvent, preprocessing of the precursor fiber material, nitridation of complex fibers, and pore-forming and pore-expansion through activation. The preparation method is simple in technique and convenient to operate and is easy to realize the uniform distribution of nanoscale catalyst particles in hollow carbon fibers. A prepared anode material tube is hollow internally, a plurality of holes are formed on the wall of the tube, and metal nitride catalysts are uniformly distributed in the three-dimensional holes of the wall of the tube, so that high specific surface area provides a sufficient place for the reaction of the battery, and the hollow pore passage in the tube can ensure an oxygen diffusion channel to be smooth and has good ion transport capacity and electrical conductivity. According to the invention, the charge-discharge capacity of the Li-air battery can be improved effectively, the power multiplying performance and the power density of the Li-air battery can be improved, the internal resistance of the battery can be reduced, and the charge-discharge polarization can be lessened through the uniform distribution of the nanoscale metal nitride, therefore, the micro-nano-structure anode material has good industrialization prospect.
Description
Technical field
The invention belongs to new energy field, relate to a kind of lithium-air battery with positive electrode and preparation method thereof.
Background technology
Along with development of human society, the becoming increasingly conspicuous of problems such as energy shortage, environmental pollution, people are to the understanding of chemical power source and require also increasingly highly, and impelling people constantly to explore new chemical power source is main energy storage system.In recent decades, with the lithium metal be the developing direction that basic battery has led the high-performance chemical power supply.Along with the successful commercialization of lithium ion battery, countries in the world are all in the research that steps up to carry out automobile-used lithium-ion-power cell.But because factors such as energy density, fail safe, prices, conventional lithium ion battery can't satisfy the requirement of electric automobile as power source.
Lithium-air battery be a kind of be negative pole with the lithium metal, air (oxygen) is as the battery of positive active material.Discharge process: the lithium in the negative pole becomes lithium cation after discharging electronics, and lithium ion passes electrolyte, combines to generate lithia or lithium peroxide with oxygen and from the electronics that external circuit flows through anodal, and stays positive pole.Charging process: through the external circuit lead electronics is provided, lithium ion passes electrolyte by positive pole and arrives negative terminal surface, and at the negative terminal surface generation lithium metal that reacts, the oxonium ion reaction generates oxygen, and the electronics of generation is supplied to lead.The energy that 1 kilogram of lithium metal of oxidation can be emitted 11680Wh in the lithium-air battery is the octuple of zinc-air cell, match in excellence or beauty in the 13000Wh/Kg of oil, and anode reactant oxygen is from environment, to obtain, and need not to store.Therefore, lithium-air battery with its high specific capacity and specific energy, environmentally friendly, be prone to characteristic such as miniaturization and lightweight and become the power conversion system that receives much concern at present, also be considered to the first-selected power source of power vehicle of future generation.
The subject matter of restriction lithium-air battery development has at present: product is insoluble to organic electrolyte in the discharge process, is prone to the deposition at positive pole, serious polarization problem in the transmission channel of obstruction oxygen and the charge and discharge process.
In theory, the population size of lithium-air battery and energy density are limited by the amount of lithium metal only.Yet because discharging product lithium peroxide solubility in organic electrolyte is very low, be deposited on the air electrode surface, stopped up the duct of carrier material, blocked contacting of oxygen and electrolyte, make discharge off, the capacity of battery brings into play and has a greatly reduced quality.Though and catalyst is not participated in cell reaction, determined the charging/discharging voltage and the efficiency for charge-discharge of battery, also can influence the invertibity of battery.Exploitation and design the anodal carrier material of novel air with efficient composite catalyst has profound significance to the development of lithium-air battery.
At present, the air positive pole of lithium-air battery generally selects for use material with carbon element as catalyst carrier.In order to improve lithium-air battery anodal specific area and utilance thereof, improve the capacity performance of battery, the researcher selects the material with carbon element of different structure, adds catalyst with the different mode of loadings that comes, thereby carries out the research to lithium-air battery.Wu Xu (electrochemical society periodical " Journal of The Electorchemical Society " 157 (2010) A294-A297) etc. are catalyst carrier with KB carbon, with catalyst MnO
2Make positive pole with the active carbon ball mill mixing, the voltage polarizing of material has some improvement, but the duct blocks easily in the discharge process, and capacity is very little; (electrochemistry communication " Electrochemistry Communications " 13 (2011) 698-700) such as Li Jiaxin with CNT as carrier, with infusion process load MnO
2Catalyst, discharge capacity rises to 1768mAh/g, and charging platform decreases, and twines seriously because the carbon pipe is reunited, and catalyst and carbon pipe can not be evenly compound, and catalyst particle size is bigger, can not bring into play high electrochemical performance; Taek Han Yong (research in nanotechnology news flash " Nanoscale Research Letters " 7 (2012)) etc. with hydro thermal method with Co
3O
4Be compound to the carbon tube-surface as positive electrode, show discharge capacity and lower overpotential preferably, but when high rate charge-discharge, the battery capacity performance sharply reduces; Zhou Haoshen (5 (2011) 3020-3026 of american chemical association " ACS Nano ") etc. are carrier with the Graphene; Not only discharge capacity is greatly improved; Simultaneously owing to the Graphene specific microstructure has high reaction activity and high; Show good catalytic effect, but the complicated synthesis technique of Graphene hinders its promotion and application in lithium-air battery with expensive cost.
Chinese patent CN 102240574A discloses a kind of catalyst of being made up of transient metal complex and carbon black support; The lithium-air battery that uses this Preparation of Catalyst to become shows fine catalytic activity and stability; But the behavior that discharges and recharges of battery is undesirable under high current density, and the hydro thermal method of employing can not be controlled the catalyst pattern; Chinese patent CN 102306808A discloses a kind of air electrode and has used catalyst to be raw material with manganese salt, silver salt; With the material with carbon element is carrier, ball mill mixing, and preparation method and process are simple to operation; But the skewness of catalyst on carrier causes catalytic effect not obvious.
In sum; This area presses for the air positive electrode of a kind of high-efficient carrier catalyst of exploitation, effectively improves discharging product when guaranteeing height ratio capacity and stops up the oxygen diffusion passage, improves the high rate performance of battery; Have high reactivity, reduce electrode polarization.
Summary of the invention
The object of the present invention is to provide a kind of lithium-air battery to use the micro-nano structure positive electrode; Prepared material had both had high specific area provides sufficient reacting environment, and the even distribution that catalyst can be in the carbon fiber tube wall simultaneously can effectively improve the reactivity of material; But this material available energy guarantees the diffusion of oxygen; Improve the high rate performance of battery, have high reactivity, reduce electrode polarization.
Another object of the present invention aims to provide simple, easy to operate preparation technology's method of above-mentioned material.
A kind of lithium-air battery of the present invention is used the micro-nano structure positive electrode, is hollow porous composite fibre, is by metal nitride catalyst agent nano particle, with the length of hollow structure be that micron-sized carbon fibre carrier is composited; Said carbon fiber tube wall is made up of a plurality of nano apertures, and connects each other between a plurality of nano aperture; The metal nitride spread loads is in carbon fiber pipe wall surface and nano aperture thereof.
Hollow structure of the present invention is the hollow duct of running through whole carbon fiber length direction.Therefore, material of the present invention is a hollow in a kind of tube wall porous, the pipe, original position composite Nano level metal nitride catalyst agent particle in tube wall surface and the hole thereof.Prepared material had both had high specific area provides sufficient reacting environment; The even distribution of nano level metal nitride catalyst in the carbon fiber tube wall simultaneously; Can effectively improve the reactivity of material; The tubular construction of hollow can guarantee the diffusion of oxygen again, has good conductivity concurrently, can effectively improve the electrode discharge capacity, improve the high rate performance and the power density that discharge and recharge polarization and battery.
Preparation method of the present invention comprises the steps:
The first step: the original position spinning preparation of carbon/catalyst precursor doughnut precursor
1, high carbon polymer mixes with organic solvent, and heated and stirred forms the polymer latex liquid solution;
2, add catalyst precursor in the polymer latex liquid solution, heated and stirred forms spinning solution;
3, spinning solution gets carbon/catalyst precursor doughnut precursor through electrostatic spinning.
Second step: the preliminary treatment of fiber precursor
First step products therefrom is carried out the low-temperature heat preliminary treatment under inert gas, to form the ladder polymer of Heat stability is good, 100～300 ℃ of low-temperature heat pretreatment temperatures;
The 3rd the step: with second the step products therefrom under nitrogen containing atmosphere to composite fibre in the metal precursor high-temperature ammonolysis; Make carbon fiber/metal nitride hollow composite fibre, further activation makes micro-nano structure carbon fiber/metal nitride hollow porous composite fibre then.
The present invention---a kind of lithium-air battery is with the interior hollow of the prepared tubes of material of the preparation method of micro-nano structure positive electrode; Tube wall contains abundant nanoscale duct; Nano aperture connects and is opened on carbon fiber surface each other, and nano level metal nitride catalyst particle high degree of dispersion is in carbon fiber tube wall and hole thereof.
Material external diameter of the present invention is 20nm～10 μ m, and boss ratio is 1/4～1/10.The length of carbon fiber is 1 μ m～1000 μ m.Whole nano aperture distribution proportion is 20%～60% for the 2-50nm mesopore accounts in the aperture of nano aperture in the carbon fiber tube wall.
Material of the present invention is owing to have a plurality of abundant three-dimensional nano apertures, thereby its carbon fiber specific area is 300m
2/ g～2000m
2/ g.
Catalyst particle size is between 10nm～100nm.
In the first step of the present invention, said polymer latex liquid solution medium high carbon polymer weight concentration is 0.1%～60%; Said catalyst or its slaine presoma and high carbon polymer proportion are 1/100～100/1.
In the first step 1 of the present invention, said high carbon polymer is one or more in the high molecular polymers (said high carbon polymer weight average molecular weight is 60000～300000) such as polyacrylonitrile, polyaniline, PEO, dimethyl sulfoxide (DMSO), polyphenyl imipramine, polyethylene, polyethylene glycol oxide, polystyrene, poly terephthalic acid benzene diester, pitch, butadiene-styrene rubber.Said solvent is volatile carrene, chloroform, acetone, one or more in not volatile formic acid, dimethyl methyl phthalein amine, the dimethyl methyl phthalein amine.
Metal nitride catalyst agent described in the present invention comprises one or more in molybdenum nitride, nitrided iron, vanadium nitride, titanium nitride, cobalt nitride, the nickel oxide.
The presoma of described metal nitride comprises one or more in the organic polymer of nitrate, ammonium salt, carbonate, sulfate, villaumite, metal of metal.
In the 3rd step of the present invention, described metal oxide nitride process, 500 ℃～1000 ℃ of nitriding temperatures.Reach 1 ℃/min of the heating rate～10 ℃/min of required nitriding temperature, temperature retention time 1h～5h, protective atmosphere are the mist of ammonia or nitrogen+hydrogen.
Described activation method comprises the physically activated of water vapour, carbon dioxide, KOH, H
3PO
4, ZnCl
2Chemical activation, or physical-chemical associating activation.
A kind of lithium-air battery of the present invention has the following advantages with the prepared micro-nano structure positive electrode of the preparation method of micro-nano structure positive electrode:
(1) original position of catalyst and carrier carbon material is compound, makes catalyst efficiently to be dispersed on the carrier, and the controllable appearance and size of catalyst can provide better battery performance simultaneously;
(2) metal nitride has the catalytic capability of similar platinum, can play good catalytic effect to the reduction of lithium-air battery positive active material oxygen, significantly improves the discharge platform of battery, reduces battery polarization;
(3) in the process of metal oxide nitride, carbon fiber equally can be by nitrogenize under ammonia atmosphere, and carbon fiber surface part carbon can be replaced by nitrogen, and carbon fiber can show higher activity after nitrogen mixed;
(4) tube wall of carbon fiber three-D pore structure is that cell reaction provides the place; Have more three-phase reaction interface; The three-D nano hole of tube wall is as the memory space of catalyst; Can realize the nanometerization of catalyst granules, and the inner hollow duct of running through whole carbon fiber does not have the product accumulation when discharge, it is unimpeded to guarantee all the time that oxygen transports; The three-dimension hole of cavity and perforation is that the transmission of ion provides short distance, transmission channel easily, thereby helps the high efficiency of transmission of lithium ion in composite inner, can obtain good electrochemical, particularly big high rate performance;
(5) preparation technology's simple possible is fit to suitability for industrialized production;
(6) raw material sources are extensive.
In sum; Process of the present invention is simple, easy to operate, and described preparation method has realized that the original position that nano level metal nitride catalyst agent uniform particles is distributed on the hollow carbon fiber is compound, hollow, tube wall porous in the prepared tubes of material; And catalyst is evenly distributed in the three-dimensional hole of tube wall; Can the unimpeded of oxygen diffusion passage be can guarantee again for cell reaction provides enough places, good ion transfer ability and conductivity had concurrently.Can effectively improve the charge/discharge capacity of lithium-air battery, reduce discharging and recharging polarization, improve the high rate performance and the power density of lithium-air battery, reduce the internal resistance of cell, industrialization prospect is good.
Description of drawings
Fig. 1 is the nitrogen adsorption curve of the positive electrode that obtains by embodiment 1.
Fig. 2 is the lithium-air battery curve of double curvature figure that obtains by embodiment 1.
Fig. 3 schemes by embodiment 2 prepared positive electrode SEM.
Fig. 4 schemes by embodiment 2 prepared positive electrode TEM.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but be not restricted to the protection range of invention.
Embodiment 1
Take by weighing 1.8g polyacrylonitrile (PAN); Add 15mL N, dinethylformamide (DMF) is at 60 ℃ of stirred in water bath 3h; Add the 5g ammonium molybdate then; Stir 1h, receive apart from 15cm, flow rate of liquid 30 μ l/min between control voltage 11kV, the two poles of the earth, obtain PAN/ ammonium molybdate doughnut through the electrostatic spinning process.The composite fibre that obtains is put into tube furnace, at 250 ℃ of following preliminary treatment 1h.Under ammonia atmosphere, 800 ℃ of nitriding temperatures, 3 ℃/min of heating rate carries out nitrogenize to the hollow composite fibre, obtains hollow carbon/molybdenum nitride composite fibre.The gained material is mixed with potassium hydroxide in proportion at 1: 4, and under argon shield, 800 ℃ of following chemical activation 2h change logical CO then
2Gas is physically activated, and insulation 1h obtains porous hollow carbon/molybdenum nitride fiber.
Pole piece preparation, battery assembling with test are: with level porous hollow carbon fiber and conductive carbon and bonding agent by being mixed and made into positive pole at 80: 10: 10; Pole piece strikes out the electrode slice that diameter is 10mm; With the metal lithium sheet is negative pole; At electrolyte is 1M LiTFSI/PC:EC (1: 1), in being full of the glove box of argon gas, is assembled into the CR2025 button cell.(25 ℃) are with 0.1mA/cm under room temperature
2In pure oxygen environment, carry out the constant current charge-discharge test, discharging and recharging cut-ff voltage is 2～4.5V.As shown in Figure 1, the composite fibre positive electrode specific area that obtains reaches 550m
2/ g.As shown in Figure 2,0.1mA/cm
2Under the current density, specific discharge capacity is 4526mAh/g, and discharge voltage plateau is increased to 3.0V; When current density increases to 0.5mA/cm
2The time, discharge capacity still reaches 2750mAh/g.
Embodiment 2
Take by weighing 1.8g polyacrylonitrile (PAN); Add 15mL N, dinethylformamide (DMF) is at 60 ℃ of stirred in water bath 3h; Add the 1g ammonium molybdate then; Stir 1h, receive apart from 15cm, flow rate of liquid 30 μ l/min between control voltage 11kV, the two poles of the earth, obtain PAN/ ammonium molybdate doughnut through the electrostatic spinning process.The composite fibre that obtains is put into tube furnace, at 250 ℃ of following preliminary treatment 1h.Under ammonia atmosphere, 800 ℃ of nitriding temperatures, 3 ℃/min of heating rate carries out nitrogenize to the hollow composite fibre, obtains hollow carbon/molybdenum nitride composite fibre.The gained material is mixed with potassium hydroxide in proportion at 1: 4, and under argon shield, 800 ℃ of following chemical activation 2h change logical CO then
2Gas is physically activated, and insulation 1h obtains porous hollow carbon/molybdenum nitride fiber.
Pole piece prepares, the battery assembling is identical with embodiment 1 with test.Along with the minimizing of catalyst loadings, the discharge capacity of battery has certain reduction, and discharge capacity is 3800mAh/g first, and the conductivity of pole piece increases.Prepared anode composite material SEM and TEM figure are like Fig. 3, Fig. 4.Can find out that by SEM figure the pattern of composite material is fibrous, length is micron order.TEM figure can find out that composite material is a hollow structure, and area load has the nm-class catalyst particle.
Embodiment 3
Take by weighing 1.8g polyacrylonitrile (PAN); Add 15mL N, dinethylformamide (DMF) is at 60 ℃ of stirred in water bath 3h; Add the 5g ammonium molybdate then; Stir 1h, receive apart from 15cm, flow rate of liquid 30 μ l/min between control voltage 11kV, the two poles of the earth, obtain PAN/ ammonium molybdate doughnut through the electrostatic spinning process.The composite fibre that obtains is put into tube furnace, at 250 ℃ of following preliminary treatment 1h.Under ammonia atmosphere, 800 ℃ of nitriding temperatures, 3 ℃/min of heating rate carries out nitrogenize to the hollow composite fibre, obtains hollow carbon/molybdenum nitride composite fibre.The gained material is mixed with KOH in proportion at 1: 4, and under argon shield, 800 ℃ of following chemical activation 2h obtain porous hollow carbon/molybdenum nitride fiber.
Pole piece prepares, the battery assembling is identical with embodiment 1 with test.The positive electrode specific area that obtains is smaller than material among the embodiment 1, is 480m
2/ g, mesopore volume reduces, and the pore volume of material is lower than employing physical-chemical associating activation gained material among the embodiment 1 behind the chemical activation.
Embodiment 4
Take by weighing 1.8g polyacrylonitrile (PAN); Add 15mLN; Dinethylformamide (DMF) at 60 ℃ of stirred in water bath 3h, adds iron chloride (accounting for the 0.5wt% of PAN quality) then and continues to stir 1h; Receive apart from 15cm, flow rate of liquid 30 μ l/min between control voltage 11kV, the two poles of the earth, obtain PAN/ iron chloride doughnut through the electrostatic spinning process.The composite fibre that obtains is put into tube furnace, at 300 ℃ of following preliminary treatment 1h.Under ammonia atmosphere, 800 ℃ of nitriding temperatures, 3 ℃/min of heating rate carries out nitrogenize to hollow carbon/iron chloride fiber, obtains hollow carbon/nitrided iron composite fibre.The gained material is mixed with KOH in proportion at 1: 4, and under argon shield, 800 ℃ of following chemical activation 2h obtain porous hollow carbon/nitrided iron fiber.
Pole piece prepares, the battery assembling is identical with embodiment 1 with test.The nanoscale nitrided iron effectively is dispersed in carbon fiber surface, and catalytic effect is good.
Embodiment 5
Take by weighing 1.8g polyacrylonitrile (PAN); Add 15mL N, dinethylformamide (DMF) is at 60 ℃ of stirred in water bath 3h; Press cobalt molybdenum mol ratio 0.8 then and add cobalt nitrate and ammonium molybdate; Continue to stir 1h, receive apart from 15cm, flow rate of liquid 30 μ l/min between control voltage 11kV, the two poles of the earth, obtain PAN/ cobalt molybdenum salt doughnut through the electrostatic spinning process.The composite fibre that obtains is put into tube furnace, at 300 ℃ of following preliminary treatment 1h.Under ammonia atmosphere, 800 ℃ of nitriding temperatures, 3 ℃/min of heating rate carries out nitrogenize to the hollow composite fibre, obtains hollow carbon/cobalt molybdenum bimetallic nitride composite fibre.The gained material is mixed with KOH in proportion at 1: 4, and under argon shield, 800 ℃ of following chemical activation 2h obtain porous hollow carbon/cobalt molybdenum bimetallic nitride fiber.
Pole piece prepares, the battery assembling is identical with embodiment 1 with test.Behind the original position load cobalt molybdenum nitride, the charging/discharging voltage platform of battery all has improvement, and polarization reduces.
Claims (14)
1. a lithium-air battery is used the micro-nano structure positive electrode, it is characterized in that: said positive electrode is a hollow porous composite fibre, is by metal nitride catalyst agent nano particle, with the length of hollow structure be that micron-sized carbon fibre carrier is composited; Said carbon fiber tube wall is made up of a plurality of nano apertures, and connects each other between a plurality of nano aperture; The metal nitride spread loads is in carbon fiber pipe wall surface and nano aperture thereof.
2. according to the said positive electrode of claim 1, it is characterized in that: described carbon fiber external diameter is 20nm～10 μ m, and boss ratio is 1/4～1/10.
3. according to the said positive electrode of claim 1, it is characterized in that: the carbon fiber specific area is 300m
2/ g～2000m
2/ g.
4. according to the said positive electrode of claim 3, it is characterized in that: carbon fiber tube wall mesopore directly is distributed as the ratio 20%～60% of the shared whole nano aperture of nano aperture of 2nm-50nm, and catalyst particle size is between 10nm～100nm.
5. according to the said positive electrode of claim 1, it is characterized in that: described metal nitride catalyst agent comprises one or more in molybdenum nitride, nitrided iron, vanadium nitride, titanium nitride, cobalt nitride, the nickel oxide.
6. the described a kind of lithium-air battery of claim 1 is with the preparation method of micro-nano structure positive electrode, and it is characterized in that: the preparation method comprises the steps:
(1) high carbon polymer is dissolved in the organic solvent, heated and stirred forms the polymer latex liquid solution; In solution, add the presoma of metal nitride catalyst agent, stir, obtain spinning solution;
(2) spinning solution obtains the compound precursor of hollow through electrostatic spinning;
(3) the compound precursor of hollow makes thermally-stabilised good carbon fiber/catalyst precursor hollow composite fibre through the low temperature preliminary treatment;
(4) under nitrogen containing atmosphere to composite fibre in the metal oxide high-temperature ammonolysis, make carbon fiber/metal nitride hollow composite fibre, further activation makes micro-nano structure carbon fiber/metal nitride hollow porous composite fibre then.
7. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: described metal nitride catalyst agent comprises one or more in molybdenum nitride, nitrided iron, vanadium nitride, titanium nitride, cobalt nitride, the nickel oxide.
8. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: the presoma of described metal nitride comprises one or more in the organic polymer of the nitrate of metal, ammonium salt, carbonate, sulfate, villaumite, metal.
9. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: described low temperature pretreatment temperature is 100 ℃～300 ℃.
According to claim 6 or 9 described a kind of lithium-air batteries with the preparation method of micro-nano structure positive electrode, it is characterized in that: nitriding temperature is 500 ℃～1000 ℃ in the described metal oxide high-temperature ammonolysis process.
11. a kind of lithium-air battery according to claim 10 is with the preparation method of micro-nano structure positive electrode; It is characterized in that: 1 ℃/min of the heating rate～10 ℃/min that reaches required nitriding temperature; Temperature retention time 1h～5h, protective atmosphere are the mist of ammonia or nitrogen+hydrogen.
12. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: described activation method comprises the physically activated of water vapour, carbon dioxide, KOH, H
3PO
4, ZnCl
2Chemical activation, or physical-chemical associating activation, protective atmosphere is at least a in nitrogen, the argon gas.
13. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: said polymer latex liquid solution medium high carbon polymer weight concentration is 0.1%～60%; Said metal nitride catalyst agent presoma salt and high carbon polymer proportion are 1/100～100/1.
14. a kind of lithium-air battery according to claim 6 is characterized in that with the preparation method of micro-nano structure positive electrode: said high carbon polymer is one or more in the high molecular polymers such as polyacrylonitrile, polyaniline, PEO, dimethyl sulfoxide (DMSO), polyphenyl imipramine, polyethylene, polyethylene glycol oxide, polystyrene, poly terephthalic acid benzene diester, pitch, butadiene-styrene rubber; Said solvent is volatile carrene, chloroform, acetone, one or more in not volatile formic acid, dimethyl methyl phthalein amine, the dimethyl methyl phthalein amine.
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