CN109830682A - A kind of preparation method and application method of high capacity aluminum cell positive electrode - Google Patents

A kind of preparation method and application method of high capacity aluminum cell positive electrode Download PDF

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CN109830682A
CN109830682A CN201910103751.9A CN201910103751A CN109830682A CN 109830682 A CN109830682 A CN 109830682A CN 201910103751 A CN201910103751 A CN 201910103751A CN 109830682 A CN109830682 A CN 109830682A
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positive electrode
aluminum cell
carbon fiber
graphene oxide
high capacity
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CN109830682B (en
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高炳亮
李启明
刘成员
刘智伟
牛宏坤
王兆文
胡宪伟
石忠宁
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Northeastern University China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of preparation method and application method of high capacity aluminum cell positive electrode, the preparation method comprises the following steps: graphene oxide-carbon fiber film is made using droplet casting method or vacuum filtration process in (1)；(2) dry under 120~200 DEG C and vacuum condition after dry under the conditions of room temperature~70 DEG C；(3) dry film is immersed in hydroiodic acid solution and is restored, washing alcohol is dry after washing；Or 300~500 DEG C of heat preservations are heated in inert atmosphere；Or it is placed in reducing atmosphere and is heated to 800~1000 DEG C of heat preservations；(4) apply microwave treatment；Application method are as follows: use positive electrode as anode using high capacity aluminum cell, anode, cathode, electrode diaphragm and electrolyte are assembled into aluminum cell.For positive electrode of the invention in charge and discharge process, electrochemical reaction is chloride ion [Cl]‑Insertion it is embedding go out to react, theoretical capacity may be up to 2231mAhg‑1, actual specific volume metric density reaches 300~1200mAhg‑1。

Description

A kind of preparation method and application method of high capacity aluminum cell positive electrode
Technical field
The invention belongs to aluminum cell technical field, in particular to a kind of preparation method of high capacity aluminum cell positive electrode And application method.
Background technique
Metallic aluminium is a kind of cell negative electrode material haveing excellent performance, and specific discharge capacity density can reach 2980mAhg-1, Volume and capacity ratio density is up to 8040mAhcm-3；Up to the present aluminum cell is not commercialized also, lie substantially in laboratory and grind Study carefully the stage, hinders the major obstacle of commercialization to be: the specific discharge capacity of the positive electrode of the aluminum cell of existing high working voltage Density is no more than 150mAhg-1；The operating voltage of the aluminum cell of positive electrode with high quality specific volume metric density is not usually high In 1V, and the cyclical stability of battery is poor；Used electrolyte is generally expensive；What these factors caused to have studied The specific energy density of aluminum cell is no more than 60Whkg-1, it is far below lithium ion battery, it is suitable with lead-acid battery, but cost is far high In lead-acid battery；Therefore, select a kind of suitable cell positive material particularly important.
Paranthaman et al. reports useIt the use of molar ratio is 2:1's for cell positive material AlCl3The discharge capacity of/[EMIm] Cl electrolyte, the battery reaches 400mAhg-1, energy density reach 1060Whkg-1, circulation After 50 circles, discharge capacity remains 50%；Jayaprakash et al. reports the uniform V using synthesis2O5Nano wire is electricity Pond positive electrode, is the room temperature fused salt electrolyte of 1.1:1 using molar ratio, and the discharge capacity of the battery is after the circle of circulation 20 273mAh·g-1；Though above-mentioned show higher specific volume metric density and ratio using the battery that transition metal oxide is positive electrode Energy density, but the cycle life of battery and coulombic efficiency are very poor；Donahue et al. is reported using FeCl3Just for battery Pole material, AlCl3/ [EMIm] Cl is the aluminum cell of electrolyte；Suto et al. is reported using VCl3For cell positive material, Room temperature fused salt is the aluminum cell of electrolyte；Koura. it reports using FeS2It the use of room temperature fused salt is electricity for cell positive material Xie Zhi；It is cell positive material that Wang et al., which is reported using 3D porous C uS, and room temperature fused salt is the battery of electrolyte；It is above-mentioned The sulfide or chloride used is the aluminum cell of positive electrode, since its positive electrode can be dissolved into electrolyte, is caused anti- The poor circulation answered, poorly reversible, coulombic efficiency is low, it is hindered further to develop.
Compare with other positive electrodes, carbon-based positive electrode is resourceful, cost is relatively low, stable structure and not with electrolyte Side reaction occurs, there is more excellent cycle performance and high rate performance using the battery that this material assembles；But pyrolysis stone Ink is prepared by chemical vapour deposition technique, and entire process flow is complicated, and the battery performance shown is relatively poor；Carbon-based material It is modified by distinct methods, its battery performance can be promoted to a certain extent, but theoretical capacity is limited, hinders Its application in commercialization aluminum cell.
Summary of the invention
For the above problem existing for existing aluminum cell positive electrode technology, the present invention provides a kind of high capacity aluminum cell use The preparation method and application method of positive electrode, are restored in mixed acid or inert atmosphere by graphene oxide and carbon fiber Heating and thermal insulation reduction or high-temperature hydrogen reduction, then microwave treatment, are made the positive electrode that can be used for high capacity aluminum cell, this is just Pole material, which is assembled into aluminum cell, can significantly improve the performance of aluminum cell, and be able to use low price electrolyte.
The preparation method of high capacity aluminum cell positive electrode of the invention sequentially includes the following steps:
1, using droplet casting method or vacuum filtration process, graphite oxide is made with graphene oxide aqueous dispersion liquid and carbon fiber Alkene-carbon fiber film；The concentration of the graphene oxide aqueous dispersion liquid is 1~5mg/mL, the diameter of the carbon fiber ≤10μm；
2, graphene oxide-carbon fiber film is dried to 30~60min under the conditions of room temperature~70 DEG C, then 120~200 DEG C and vacuum condition under dry 12~for 24 hours, dry film is made；
3, will dry film immerse hydroiodic acid solution in, 40~100 DEG C restore 1~for 24 hours, be then washed with deionized water The acid solution on surface, then wash away with dehydrated alcohol the moisture on surface, finally dry 12 under 120~200 DEG C and vacuum condition~ For 24 hours, weak reduction film is made；Or dry film is placed under inert atmosphere conditions, be heated to 300~500 DEG C heat preservation 0.5~ Weak reduction film is made in 2h；Or dry film is placed under reducing atmosphere condition, be heated to 800~1000 DEG C heat preservation 10~ Weak reduction film is made in 30min；The reducing atmosphere is hydrogen argon gas mixed atmosphere, and wherein the percent by volume of hydrogen is 5 ~10%；The mass concentration of HI is 55~58% in the hydroiodic acid solution；The inert atmosphere is nitrogen atmosphere or argon Gas atmosphere；
4, weak reduction film is placed in micro-wave oven, under the conditions of argon atmosphere, applies 1~50s of microwave treatment, height is made Capacity aluminum cell positive electrode.
Above-mentioned droplet casting method is that carbon fiber is placed on cellulose filter membrane, and graphene oxide aqueous dispersion liquid is added dropwise On carbon fiber, graphene oxide is compound with carbon fiber；The vacuum filtration process is that carbon fiber is placed on cellulose filter membrane, It is then placed in funnel, after graphene oxide aqueous dispersion liquid is added, graphene oxide is compound with carbon fiber, while part water It is separated by filtering.
The purity of above-mentioned nitrogen and argon gas is >=99.999%.
Above-mentioned high capacity aluminum cell positive electrode is strong redox graphene-carbon fiber film (SrGO-CF).
In the above method, the amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber is by graphene oxide and carbon fiber Mass ratio is (1~10): 1.
In above-mentioned step 2,3 or 4, vacuum condition is pressure≤200Pa.
The application method of high capacity aluminum cell positive electrode of the invention are as follows:
Use positive electrode as anode using high capacity aluminum cell, using aluminium foil as cathode, using glass fiber filter paper As electrode diaphragm, anode, cathode, electrode diaphragm and electrolyte are assembled into aluminum cell.
Above-mentioned electrolyte is AlCl3- EMIC (1- ethyl -3- methylimidazolium chloride), AlCl3Acetamide, AlCl3Urine Element, AlCl3Propionamide or AlCl3Butyramide；AlCl in electrolyte3Molar percentage be 52~67%.
In the above method, the contact conductor material that aluminum cell uses is assembled into as carbon cloth, metal molybdenum, tungsten or is attached with The metal foil of titanium nitride coating；Wherein the material of metal foil is metallic nickel, stainless steel, metallic copper, metallic aluminium or Titanium.
Additive is added in above-mentioned electrolyte, additive accounts for the 1~10% of electrolyte total mole number, and additive is selected LiCl, LiBr, NaCl, NaBr, EC (ethylene carbonate), THF (tetrahydrofuran) or DCE (1,2- dichloroethanes).
0.5~0.8V of average working voltage of above-mentioned aluminum cell, specific discharge capacity are 300~1200mAhg-1, quality Specific energy is 150~960Whkg-1。
Compared with prior art, the advantages of method of the invention, is with beneficial effect:
In battery charge and discharge process, the electrochemical reaction of generation is usually the carbonaceous positive electrode of prior art [AlCl4]-The insertion of ion and embedding reaction out, due to [AlCl4]-Ion size is larger, therefore the theoretical ratio of these positive electrodes Capacity density is difficult more than 150mAhg-1, actual specific volume metric density is usually in 100mAhg-1；Positive material of the invention For material in charge and discharge process, electrochemical reaction is chloride ion [Cl]-Insertion it is embedding go out to react, theoretical capacity may be up to 2231mAh·g-1, actual specific volume metric density reaches 300~1200mAhg-1。
Detailed description of the invention
Fig. 1 is the high capacity aluminum cell positive electrode in the embodiment of the present invention 1 in AlCl3Following in-EMIC electrolyte Ring volt-ampere curve figure；
Fig. 2 is the charging and discharging curve figure of the aluminum cell assembled in the embodiment of the present invention 1；In figure, ■ is charging, ● to put Electricity.
Specific embodiment
Graphene oxide (GO) aqueous dispersion liquid used in the embodiment of the present invention is commercial products.
The single layer rate of graphene oxide in graphene oxide (GO) aqueous dispersion liquid used in the embodiment of the present invention >= 99%.
The carbon fiber used in the embodiment of the present invention is commercially available chopped carbon fiber, using preceding in 120~200 DEG C and vacuum degree Dry 12 under the conditions of≤50Pa~for 24 hours.
The hydroiodic acid (HI) used in the embodiment of the present invention for commercially available reagent (mass fraction 55.0-58.0%, containing≤ 1.5%H3PO2Stabilizer), it is protected from light, saved under low temperature.
The anhydrous AlCl that electrolyte uses purity > 99% is prepared in the embodiment of the present invention3, using preposition in argon atmosphere It is saved backup in glove box.
LiCl, LiBr, NaCl, NaBr, EC (ethylene carbonate) for being used in the embodiment of the present invention, THF (tetrahydrofuran), DCE (1,2- dichloroethanes) is market analytical pure reagents, using preceding dry 24 under the conditions of vacuum degree≤50Pa and 60-120 DEG C ~36h, is placed in the glove box of argon atmosphere and saves backup.
EMIC (1- ethyl -3- methylimidazolium chloride), the acetamide, urea, propionamide, fourth used in the embodiment of the present invention Amide is commercially available reagent, using preceding 24~36h dry under the conditions of vacuum degree≤50Pa and 60-120 DEG C, is placed in argon atmosphere Glove box in save backup.
The carbon cloth that uses in the embodiment of the present invention, metal molybdenum, tungsten and the metal foil of titanium nitride coating is attached with as city Purchase product, purity >=99.9%；Use preceding removing surface impurity.The preparation method of titanium carbide coating such as text in the embodiment of the present invention Offer " Adv.Sci.2018,5,1700712: earth element abundant prepares flexible current-collecting body for aluminium chloride-graphite cell " institute It states.
The cellulose filter membrane (cellulose membranes, Whatman) used in the embodiment of the present invention is commercially available production Product, aperture≤0.22 μm.
The droplet casting equipment that droplet casting method uses in the embodiment of the present invention is dropper or pin hole syringe.
The funnel that the vacuum filtration method used in the embodiment of the present invention uses is sand core funnel.
It is that heating plate in the glove box of argon atmosphere is enterprising that inert atmosphere, which prepares weak reduction film, in step 3 of the present invention Row processing.
Dry film immerses hydroiodic acid solution in the embodiment of the present invention, is heated in oil bath, and dry film is set It is sealed in conical flask.
After dry film is placed in reducing atmosphere condition heating and thermal insulation in the embodiment of the present invention, the furnace cooling under argon atmosphere To room temperature.
Microwave treatment is carried out in the embodiment of the present invention uses household microwave oven, 800~1000W of operating power.
When carrying out microwave treatment in the embodiment of the present invention, weak reduction film is placed in the air-tight bottle full of argon gas.
The glass fiber filter paper used in the embodiment of the present invention is commercial products, using preceding in vacuum degree≤50Pa and 60- Dry 24~36h, is placed in the glove box of argon atmosphere and saves backup under the conditions of 120 DEG C.
The battery used in the embodiment of the present invention is soft-package battery.
When being assembled into aluminum cell in the embodiment of the present invention, to keep anhydrous state, carried out in the glove box of argon atmosphere Ingredient and assembled battery, with heat sealing machine by cell sealing.
Water and oxygen content are respectively less than 0.1ppm in the glove box used in the embodiment of the present invention.
In the embodiment of the present invention purity of nitrogen and argon gas >=99.999%.
The equipment that the cyclic voltammetry of battery uses in the embodiment of the present invention is Shanghai Chen Hua electrochemical workstation.
The equipment that the performance test of battery uses in the embodiment of the present invention is the new Weir battery test system in Shenzhen.
In step 2,3 or 4 of the invention, vacuum condition is pressure≤200Pa.
Embodiment 1
Using droplet casting method, graphene oxide-carbon fiber film is made with graphene oxide aqueous dispersion liquid and carbon fiber, it will Carbon fiber is placed on cellulose filter membrane, and graphene oxide and carbon on carbon fiber is added dropwise in graphene oxide aqueous dispersion liquid Fiber composite；The concentration of graphene oxide aqueous dispersion liquid is 1mg/mL, diameter≤10 μm of carbon fiber；Graphene oxide water phase The amount ratio of dispersion liquid and carbon fiber is 1:1 by the mass ratio of graphene oxide and carbon fiber；
Graphene oxide-carbon fiber film is dried into 60min at room temperature, then is done under 120 DEG C and vacuum condition It is dry for 24 hours, dry film is made；
Dry film is immersed in hydroiodic acid solution, in 40 DEG C of reductase 12 4h, the acid on surface is then washed with deionized water Liquid, then wash away with dehydrated alcohol the moisture on surface, finally under 120 DEG C and vacuum condition it is dry for 24 hours, weak reduction film is made； The mass concentration of HI is 58% in hydroiodic acid solution；
Weak reduction film is placed in micro-wave oven, under the conditions of argon atmosphere, applies microwave treatment 30s, high capacity is made Aluminum cell positive electrode；
Cyclic voltammetry, sweep speed 0.2mV/s are carried out using Shanghai Chen Hua electrochemical workstation；Cyclic voltammetric is bent Line is as shown in Figure 1；
Use positive electrode as anode using high capacity aluminum cell, using aluminium foil as cathode, using glass fiber filter paper As electrode diaphragm, anode, cathode, electrode diaphragm and electrolyte are assembled into aluminum cell；Electrolyte is AlCl3-EMIC；Electrolysis AlCl in matter3Molar percentage be 52%；The contact conductor material used is metal molybdenum；
The constant current charge-discharge test of aluminum cell is carried out using the new Weir battery test system in Shenzhen, the charge and discharge of measurement are cut Only voltage is 0.01-2.45V, 0.5~0.8V of average working voltage, current density 100mA/g, the electric discharge mass ratio of aluminum cell Capacity can achieve 800mAhg-1, specific energy 690Whkg-1, the charging and discharging curve of aluminum cell is as shown in Figure 2.
Embodiment 2
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) vacuum filtration process is used, graphene oxide-carbon fiber is made with graphene oxide aqueous dispersion liquid and carbon fiber Carbon fiber is placed on cellulose filter membrane by film, is then placed in funnel, after graphene oxide aqueous dispersion liquid is added, Graphene oxide is compound with carbon fiber, while part water is filtered and separated；The concentration of graphene oxide aqueous dispersion liquid is 2mg/ mL；The amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber is 2:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried into 55min at room temperature, then under 130 DEG C and vacuum condition Dry 22h；
(3) it in 80 DEG C of reduction 10h, washes after being washed with alcohol in 150 DEG C and 18h dry under vacuum condition；In hydroiodic acid solution The mass concentration of HI is 56%；
(4) microwave treatment 20s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Acetamide；AlCl in electrolyte3Molar percentage be 54%；The contact conductor material used is carbon cloth；
(2) current density of charge-discharge test is 110mA/g, and the electric discharge specific discharge capacity of battery can achieve 750mAh g-1, specific energy 720Whkg-1。
Embodiment 3
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) concentration of graphene oxide aqueous dispersion liquid is 2mg/mL；Graphene oxide aqueous dispersion liquid and carbon fiber Amount ratio is 3:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried into 50min at room temperature, then under 140 DEG C and vacuum condition Dry 20h；
(3) it in 100 DEG C of reduction 1h, washes after being washed with alcohol in 200 DEG C and 12h dry under vacuum condition；In hydroiodic acid solution The mass concentration of HI is 55%；
(4) microwave treatment 10s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Urea；AlCl in electrolyte3Molar percentage be 57%； The contact conductor material used is tungsten；Additive is added in electrolyte, additive accounts for the 1% of electrolyte total mole number, Additive selects LiCl；
(2) current density of charge-discharge test is 120mA/g, and the electric discharge specific discharge capacity of battery can achieve 500mAh g-1, specific energy 170Whkg-1。
Embodiment 4
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) vacuum filtration process is used, graphene oxide-carbon fiber is made with graphene oxide aqueous dispersion liquid and carbon fiber Carbon fiber is placed on cellulose filter membrane by film, is then placed in funnel, after graphene oxide aqueous dispersion liquid is added, Graphene oxide is compound with carbon fiber, while part water is filtered and separated；The concentration of graphene oxide aqueous dispersion liquid is 3mg/ mL；The amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber is 4:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 50min under the conditions of 30 DEG C, then under 150 DEG C and vacuum condition Dry 18h；
(3) dry film is placed under inert atmosphere conditions, is heated to 500 DEG C of heat preservation 0.5h, weak reduction film is made；Institute The inert atmosphere stated is nitrogen atmosphere；
(4) microwave treatment 50s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Propionamide；AlCl in electrolyte3Molar percentage be 60%；For the contact conductor material used for the metal foil for being attached with titanium nitride coating, the material of metal foil is metallic nickel；Electrolyte In be added with additive, additive accounts for the 2% of electrolyte total mole number, and additive selects LiBr；
(2) current density of charge-discharge test is 150mA/g, and the electric discharge specific discharge capacity of battery can achieve 1170mAh·g-1, specific energy 480Whkg-1。
Embodiment 5
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) concentration of graphene oxide aqueous dispersion liquid is 3mg/mL；Graphene oxide aqueous dispersion liquid and carbon fiber Amount ratio is 5:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 45min under the conditions of 40 DEG C, then under 160 DEG C and vacuum condition Dry 16h；
(3) dry film is placed under inert atmosphere conditions, is heated to 300 DEG C of heat preservation 2h, weak reduction film is made；It is described Inert atmosphere be nitrogen atmosphere；
(4) microwave treatment 3s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Butyramide；AlCl in electrolyte3Molar percentage be 63%；For the contact conductor material used for the metal foil for being attached with titanium nitride coating, the material of metal foil is stainless steel；Electrolyte In be added with additive, additive accounts for the 4% of electrolyte total mole number, and additive selects NaCl；
(2) current density of charge-discharge test is 200mA/g, and the electric discharge specific discharge capacity of battery can achieve 900mAh g-1, specific energy 330Whkg-1。
Embodiment 6
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) vacuum filtration process is used, graphene oxide-carbon fiber is made with graphene oxide aqueous dispersion liquid and carbon fiber Carbon fiber is placed on cellulose filter membrane by film, is then placed in funnel, after graphene oxide aqueous dispersion liquid is added, Graphene oxide is compound with carbon fiber, while part water is filtered and separated；The concentration of graphene oxide aqueous dispersion liquid is 4mg/ mL；The amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber is 6:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 40min under the conditions of 45 DEG C, then under 170 DEG C and vacuum condition Dry 15h；
(3) dry film is placed under inert atmosphere conditions, is heated to 400 DEG C of heat preservation 1h, weak reduction film is made；It is described Inert atmosphere be argon atmosphere；
(4) microwave treatment 40s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Butyramide；AlCl in electrolyte3Molar percentage be 65%；For the contact conductor material used for the metal foil for being attached with titanium nitride coating, the material of metal foil is metallic copper；Electrolyte In be added with additive, additive accounts for the 6% of electrolyte total mole number, and additive selects NaBr；
(2) current density of charge-discharge test is 100mA/g, and the electric discharge specific discharge capacity of battery can achieve 360mAh g-1, specific energy 950Whkg-1。
Embodiment 7
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) concentration of graphene oxide aqueous dispersion liquid is 4mg/mL；Graphene oxide aqueous dispersion liquid and carbon fiber Amount ratio is 7:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 40min under the conditions of 50 DEG C, then under 180 DEG C and vacuum condition Dry 14h；
(3) dry film is placed under reducing atmosphere condition, is heated to 800 DEG C of heat preservation 30min, weak reduction film is made； The reducing atmosphere is hydrogen argon gas mixed atmosphere, and wherein the percent by volume of hydrogen is 10%；
(4) microwave treatment 5s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Propionamide；AlCl in electrolyte3Molar percentage be 67%；For the contact conductor material used for the metal foil for being attached with titanium nitride coating, the material of metal foil is metallic aluminium；Electrolyte In be added with additive, additive accounts for the 8% of electrolyte total mole number, and additive selects EC；
(2) current density of charge-discharge test is 300mA/g, and the electric discharge specific discharge capacity of battery can achieve 600mAh g-1, specific energy 240Whkg-1。
Embodiment 8
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) vacuum filtration process is used, graphene oxide-carbon fiber is made with graphene oxide aqueous dispersion liquid and carbon fiber Carbon fiber is placed on cellulose filter membrane by film, is then placed in funnel, after graphene oxide aqueous dispersion liquid is added, Graphene oxide is compound with carbon fiber, while part water is filtered and separated；The concentration of graphene oxide aqueous dispersion liquid is 5mg/ mL；The amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber is 8:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 30min under the conditions of 60 DEG C, then under 190 DEG C and vacuum condition Dry 13h；
(3) dry film is placed under reducing atmosphere condition, is heated to 900 DEG C of heat preservation 20min, weak reduction film is made； The reducing atmosphere is hydrogen argon gas mixed atmosphere, and wherein the percent by volume of hydrogen is 8%；
(4) microwave treatment 25s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Urea；AlCl in electrolyte3Molar percentage be 66%； The contact conductor material used is the Titanium that is attached with titanium nitride coating；Additive is added in electrolyte, additive accounts for electricity The 9% of matter total mole number is solved, additive selects THF；
(2) current density of charge-discharge test is 160mA/g, and the electric discharge specific discharge capacity of battery can achieve 900mAh g-1, specific energy 710Whkg-1。
Embodiment 9
The preparation method is the same as that of Example 1 for high capacity aluminum cell positive electrode, and difference is:
(1) concentration of graphene oxide aqueous dispersion liquid is 5mg/mL；Graphene oxide aqueous dispersion liquid and carbon fiber Amount ratio is 10:1 by the mass ratio of graphene oxide and carbon fiber；
(2) graphene oxide-carbon fiber film is dried to 70min under the conditions of 70 DEG C, then under 200 DEG C and vacuum condition Dry 12h；
(3) dry film is placed under reducing atmosphere condition, is heated to 1000 DEG C of heat preservation 10min, weak reduction film is made； The reducing atmosphere is hydrogen argon gas mixed atmosphere, and wherein the percent by volume of hydrogen is 10%；
(4) microwave treatment 35s；
With embodiment 1, difference is application method:
(1) electrolyte that assembling aluminum cell uses is AlCl3Acetamide；AlCl in electrolyte3Molar percentage be 56%；The contact conductor material used is the Titanium that is attached with titanium nitride coating；Additive, additive are added in electrolyte The 10% of electrolyte total mole number is accounted for, additive selects DCE；
(2) current density of charge-discharge test is 180mA/g, and the electric discharge specific discharge capacity of battery can achieve 560mAh g-1, specific energy 460Whkg-1。

Claims (9)

1. a kind of preparation method of high capacity aluminum cell positive electrode, it is characterised in that sequentially include the following steps:
(1) droplet casting method or vacuum filtration process are used, graphene oxide-carbon is made with graphene oxide aqueous dispersion liquid and carbon fiber Fiber membrane；The concentration of the graphene oxide aqueous dispersion liquid is 1~5mg/mL, diameter≤10 μ of the carbon fiber m；
(2) graphene oxide-carbon fiber film is dried to 30~60min under the conditions of room temperature~70 DEG C, then at 120~200 DEG C With under vacuum condition dry 12~for 24 hours, dry film is made；
(3) will dry film immerse hydroiodic acid solution in, 40~100 DEG C restore 1~for 24 hours, table is then washed with deionized water The acid solution in face, then wash away with dehydrated alcohol the moisture on surface, finally dry 12 under 120~200 DEG C and vacuum condition~for 24 hours, Weak reduction film is made；Or dry film is placed under inert atmosphere conditions, 300~500 DEG C of 0.5~2h of heat preservation are heated to, Weak reduction film is made；Or dry film is placed under reducing atmosphere condition, be heated to 800~1000 DEG C heat preservation 10~ Weak reduction film is made in 30min；The reducing atmosphere is hydrogen argon gas mixed atmosphere, and wherein the percent by volume of hydrogen is 5 ~10%；The mass concentration of HI is 55~58% in the hydroiodic acid solution；The inert atmosphere is nitrogen atmosphere or argon Gas atmosphere；
(4) weak reduction film is placed in micro-wave oven, under the conditions of argon atmosphere, applies 1~50s of microwave treatment, Gao Rong is made Measure aluminum cell positive electrode.
2. a kind of preparation method of high capacity aluminum cell positive electrode according to claim 1, it is characterised in that described Droplet casting method be that carbon fiber is placed on cellulose filter membrane, by graphene oxide aqueous dispersion liquid be added dropwise on carbon fiber, oxygen Graphite alkene and carbon fiber are compound；The vacuum filtration process is that carbon fiber is placed on cellulose filter membrane, is then placed within In funnel, after graphene oxide aqueous dispersion liquid is added, graphene oxide is compound with carbon fiber, while part water is filtered and divided From.
3. a kind of preparation method of high capacity aluminum cell positive electrode according to claim 1, it is characterised in that described Nitrogen and argon gas purity >=99.999%.
4. a kind of preparation method of high capacity aluminum cell positive electrode according to claim 1, it is characterised in that step (1) in the amount ratio of graphene oxide aqueous dispersion liquid and carbon fiber by the mass ratio of graphene oxide and carbon fiber be (1~ 10):1。
5. a kind of application method of high capacity aluminum cell positive electrode, it is characterised in that the Gao Rong prepared using claim 1 Amount aluminum cell uses positive electrode as anode, will just using glass fiber filter paper as electrode diaphragm as cathode using aluminium foil Pole, cathode, electrode diaphragm and electrolyte are assembled into aluminum cell.
6. the application method of high capacity aluminum cell positive electrode according to claim 5, it is characterised in that the electricity Xie Zhiwei AlCl3-EMIC、AlCl3Acetamide, AlCl3Urea, AlCl3Propionamide or AlCl3Butyramide；In electrolyte AlCl3Molar percentage be 52~67%.
7. the application method of high capacity aluminum cell positive electrode according to claim 5, it is characterised in that be assembled into aluminium The contact conductor material that battery uses is carbon cloth, metal molybdenum, tungsten or the metal foil for being attached with titanium nitride coating；Wherein metal The material of foil is metallic nickel, stainless steel, metallic copper, metallic aluminium or Titanium.
8. the application method of high capacity aluminum cell positive electrode according to claim 5, it is characterised in that the electricity Xie Zhizhong is added with additive, and additive accounts for the 1~10% of electrolyte total mole number, additive select LiCl, LiBr, NaCl, NaBr, EC, THF or DCE.
9. the application method of high capacity aluminum cell positive electrode according to claim 5, it is characterised in that the aluminium 0.5~0.8V of average working voltage of battery, specific discharge capacity are 300~1200mAhg-1, specific energy be 150~ 960Wh·kg-1。
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