CN105406072B - A kind of battery of electrode overlay film - Google Patents

A kind of battery of electrode overlay film Download PDF

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Publication number
CN105406072B
CN105406072B CN201510902172.2A CN201510902172A CN105406072B CN 105406072 B CN105406072 B CN 105406072B CN 201510902172 A CN201510902172 A CN 201510902172A CN 105406072 B CN105406072 B CN 105406072B
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overlay film
battery
negative pole
electrode
negative
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CN105406072A (en
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闫高领
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Hebei Feibao Amperex Technology Limited
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Hebei Feibao Amperex Technology Ltd
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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
    • 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
    • H01M4/583—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of battery of electrode overlay film, belong to field of batteries.A kind of battery of electrode overlay film of the present invention, including positive plate and negative plate inside battery case, are provided with barrier film between the positive plate and negative plate；Positive pole overlay film and anode catalytic net are sequentially provided between the positive plate and barrier film, the anode catalytic net is overlying on the surface of barrier film；Negative pole catalysis net and negative pole overlay film are sequentially provided between the barrier film and negative plate, the negative pole catalysis net is overlying on the surface of barrier film；The positive plate is nanometer Rh graphene combination electrodes；The negative plate is nano Co2SnO4Polysulfonate acid naphthalene electrode；The positive pole overlay film is cell nafion proton membrane, and the negative pole overlay film is silica, and the thickness of the positive pole overlay film is 300nm, the thickness 300nm of the negative pole overlay film.The characteristics of a kind of battery of electrode overlay film of the present invention has small volume, and light weight is stable using process safety, and battery capacity is big, and electrode is not easy to be lost, and discharge performance is excellent.

Description

A kind of battery of electrode overlay film
Technical field
The present invention relates to a kind of battery, particularly a kind of battery of electrode overlay film.
Background technology
After Pu Lai get in 1859 trial-produces chemical conversion formula lead-acid accumulator successfully, electrochmical power source enters people's bud. In the evolution of more than 100 years, the electrochmical power source of new range is continuously emerged, and the performance of electrochmical power source is constantly improved.Especially It is that the development of electrochmical power source is rapider after World War II.Cd-Ni batteries, production the 1980s are generated later MH-Ni batteries have been given birth to, by the exploration of nearly 20 years, have developed lithium ion battery and lighium polymer in early 1990s finally Battery, their development have also been arrived i.e. by the stage of commercialization, and at present, lithium ion battery is with its high specific energy density and service life Grow and be taken seriously, quickly grow, lithium polymer battery is also given priority in the countries and regions such as the U.S., Japan and Taiwan.Lithium gathers The development of compound battery is swift and violent, progressively substitutes cadmium nickel and Ni-H cell, makees grinding for electrode and electrolyte using polymer It is particularly noticeable to study carefully exploitation.But the ionic conductivity and mechanical strength of current lithium polymer battery are poor, manufacturing process Complexity, battery volume is larger, and battery capacity is inadequate, because positive active material and negative electrode active material easily come off, for a long time Poor using rear ionic conductivity and electrochemical stability, isolating film strength and stability can also become with the use of battery Change, it is easy to cause lithium polymer battery aging after a long time use, the life-span of discharge and recharge is very restricted.
The content of the invention
The goal of the invention of the present invention is：For above-mentioned problem, there is provided a kind of small volume, light weight, used Journey safety and stability, battery capacity is big, and electrode is not easy to be lost, the excellent battery of discharge performance.
The technical solution adopted by the present invention is as follows：
A kind of battery of electrode overlay film of the present invention, including positive plate and negative plate inside battery case, it is described Barrier film is provided between positive plate and negative plate；Positive pole overlay film and anode catalytic are sequentially provided between the positive plate and barrier film Net, the positive pole overlay film are overlying on the surface of positive plate, and the anode catalytic net is overlying on the surface of barrier film；The barrier film is with bearing Negative pole catalysis net and negative pole overlay film are sequentially provided between pole piece, the negative pole catalysis net is overlying on the surface of barrier film, the negative pole Overlay film is overlying on the surface of negative plate；The positive plate is nanometer Rh- graphene combination electrodes；The negative plate is nano Co2SnO4 Polysulfonate acid naphthalene electrode；The positive pole overlay film is cell nafion proton membrane, and the negative pole overlay film is silica, the positive pole overlay film Thickness be 300nm, the thickness 300nm of the negative pole overlay film.
By adopting the above-described technical solution, lithium battery during discharge and recharge, can be passivated in electricity due to overload Oxide is formed on extremely, so as to cause the decline of battery capacity, the efficiency for charge-discharge of electrode reduces, in positive plate and negative plate table Face overlay film, the affinity that can be effectively improved between electrode and barrier film, increase ionic conducting property, reduce the generation of oxide, So as to the service life of the battery of extension.
From microstructure, Rh is attached on graphene nanometer sheet favorably positive plate material in porous side's laminated structure In the contact area of increase rhodium and electrolyte, the utilization rate of active material is improved, while graphene also contributes to improve material Electric conductivity, improve the battery performance of positive plate, so as to improve the operating efficiency of battery.
Negative plate material is from microstructure, Co2SnO4Mutually inlayed with polysulfonate acid naphthalene, it is three-dimensional to form three dimensions Structure, improve Co2SnO4The reunion of particle, a good space conductive network is formd, improves the cell performance of negative plate Can, so as to improve the operating efficiency of battery.
Overlay film on positive plate and negative plate surface, the affinity that can be effectively improved between electrode and barrier film, increase from Subconductivity performance, the generation of oxide is reduced, so as to the service life of the battery of extension.
A kind of battery of electrode overlay film of the present invention, the thickness of the positive plate is 40 μm；The thickness of the negative plate is 50μm；Positive plate specific capacitance of being discharged when electric current is 1A/g is 576.3F/g, and the negative plate is put when electric current is 1A/g Electric specific capacitance is 817.6F/g.
A kind of battery of electrode overlay film of the present invention, the thickness of the anode catalytic net is 10 μm, the anode catalytic net Anode catalyst is loaded with, the anode catalyst is Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymers, described The bearing capacity of the online anode catalyst of anode catalytic is 0.38mg/cm2；The thickness of the negative pole catalysis net is 10 μm, described negative Pole catalysis net is loaded with cathode catalyst, and the cathode catalyst is oligomeric cagelike silsesquioxane-graphene, and the negative pole is urged The bearing capacity for changing online cathode catalyst is 0.71mg/cm2。
By adopting the above-described technical solution, appropriate catalyst is added on positive pole and negative pole, can be in wider temperature The capacity and workbench for making battery in the range of degree are improved, particularly in low temperature and heavy-current discharge, so as to effectively Avoid Li ions from forming oxide in electrode passivation, extend the service life of battery, the catalyst that the present invention uses can ensure Battery being capable of normal work in the range of -50 ~ 60 DEG C.
A kind of battery of electrode overlay film of the present invention, the barrier film is polymer-LiClO4-Li4Ti5O12Combined electrolysis Matter, the polymer are polystyrene-ethylene pyrrolidones-styrene triblock copolymer, and the thickness of the barrier film is 40 μ m。
By adopting the above-described technical solution, polystyrene-ethylene pyrrolidones-styrene triblock copolymer is as base Matter, there is stronger polarity, and containing the group for easily forming hydrogen bond, some small molecules can be combined, improve the conduction of lithium ion Efficiency, ion conductor Li4Ti5O12The addition of nano-particle reduces the crystallinity of polymer, improves polymer dielectric Electrical conductivity, add in polymer and flowing subnumber mesh, so as to improve the operating efficiency of battery；Polystyrene-ethylene pyrrole simultaneously Pyrrolidone-styrene triblock copolymer has good elasticity, and lighter weight, from microcosmic, its molecular structure presents steady Fixed network structure, apparent activation energy are larger.
A kind of battery of electrode overlay film of the present invention, the barrier film surface are covered with coat, and the coat is poly- inclined PVF-hexafluoropropene, the thickness of the coat is 100nm.
By adopting the above-described technical solution, after coating, the tensile strength enhancing of barrier film, the adsorption capacity of electronics is increased Greatly, shrinkage factor reduces, and venting capability slightly reduces, and internal resistance is greatly lowered, so as to reduce the phenomenon production of inside battery heating It is raw, add the safety and stability performance of battery.
A kind of battery of electrode overlay film of the present invention, the Cr- di-thiofuran ethylenes base tetraazatetradecane porphyrin two dimension conjugated polymers Thing is prepared by following steps,
Step 1：Weigh a 1,2- dicyanos -1,2- two（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene, take appropriate N-amyl alcohol dissolves as stirring solvent, according to 1,2- dicyanos -1,2- bis-（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene：Vinegar Sour chromium mol ratio 1:2 add hexaaquochromium triacetate into solution, add appropriate DBU catalyst, and heating reflux reaction 20h is natural Normal temperature is cooled to, is steamed solvent by Rotary Evaporators, obtains Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin polymer；
Step 2：A Cr- di-thiofuran ethylenes base tetraazatetradecane porphyrin polymer is weighed, takes q. s. methylene chloride to make solvent, Ultrasonic wave disperses 30min, under the pressure of 5 atmospheric pressure, is put into reactor and heats 5h under conditions of 150 DEG C, naturally cold But to normal temperature, filtering, it is washed with deionized, under conditions of vacuum is 0.98, air drying 24h, obtains Cr- Dithiophenes Vinyl tetraazatetradecane porphyrin two dimension conjugated polymer.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, the affinity that can be effectively improved between electrode and barrier film, increase ionic conducting property, reduce the production of oxide It is raw, so as to the service life of the battery of extension.
2nd, can be improved within the scope of wider temperature the capacity of battery and workbench, particularly in low temperature and During heavy-current discharge, oxide is formed in electrode passivation so as to be effectively prevented from Li ions.
3rd, internal resistance is greatly lowered, and produces so as to reduce the phenomenon of inside battery heating, is gone wrong in inside battery When, timely embody, show as bulging without exploding, add the safety and stability performance of battery.
Brief description of the drawings
Fig. 1 is a kind of structural representation of polymer battery；
Fig. 2 is the SEM figures of positive plate；
Fig. 3 is the SEM figures of negative plate；
Fig. 4 is the SEM figures of polystyrene-ethylene pyrrolidones-styrene triblock copolymer.
Marked in figure：1 is positive plate, and 2 be negative plate, and 3 be anode catalytic net, and 4 be negative pole catalysis net, and 5 be barrier film, 6 It is positive pole overlay film for battery case, 7,8 be negative pole overlay film.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is described in detail.
In order that the object, technical solution and advantage of invention are more clearly understood, below in conjunction with drawings and Examples, to this Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not For limiting the present invention.
Embodiment 1
As shown in figure 1, a kind of polymer battery, including positive plate 1 and negative plate 2 inside battery case 6, positive pole Barrier film 5 is provided between piece 1 and negative plate 2；Positive pole overlay film 7 and anode catalytic net are sequentially provided between positive plate 1 and barrier film 5 3, positive pole overlay film 7 is overlying on the surface of positive plate 1, and anode catalytic net 3 is overlying on the surface of barrier film 5；Barrier film 5 and negative plate 2 it Between be sequentially provided with negative pole catalysis net 4 and negative pole overlay film 8, negative pole catalysis net 4 is overlying on the surface of barrier film 5, and negative pole overlay film 8 is overlying on negative The surface of pole piece 2, positive pole overlay film 7 connect with anode catalytic net 3, and negative pole overlay film 8 connects with negative pole catalysis net 4.
Positive plate 1 is nanometer Rh- graphene combination electrodes, and the thickness of positive plate 1 is 40 μm；Negative plate 2 is nanometer Co2SnO4Polysulfonate acid naphthalene electrode, the thickness of negative plate 2 is 50 μm；The specific capacitance of being discharged when electric current is 1A/g of positive plate 1 is 576.3F/g, the specific capacitance of being discharged when electric current is 1A/g of negative plate 2 is 817.6F/g.
The thickness of anode catalytic net 3 is 10 μm, and anode catalytic net 3 is loaded with anode catalyst, and anode catalyst is Cr- bis- Thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer, the bearing capacity of anode catalyst is 0.38mg/ on anode catalytic net 3 cm2；The thickness of negative pole catalysis net 4 is 10 μm, and negative pole catalysis net 4 is loaded with cathode catalyst, and cathode catalyst is oligomeric cage type Silsesquioxane-graphene, the bearing capacity of cathode catalyst is 0.71mg/cm on negative pole catalysis net 42。
Barrier film 5 is polymer-LiClO4-Li4Ti5O12Composite electrolyte, polymer are polystyrene-ethylene pyrrolidines Ketone-styrene triblock copolymer, the thickness of barrier film 5 is 40 μm.The surface of barrier film 5 is covered with coat, and coat is poly- inclined PVF-hexafluoropropene, the thickness of coat is 100nm.
Positive pole overlay film 6 is cell nafion proton membrane, and negative pole overlay film 7 is silica, and the thickness of positive pole overlay film 6 is 300nm, The thickness 300nm of negative pole overlay film 7.
Battery case 6 is made up of soft plastic, and soft plastic includes dimethicone 18.5%, talcum powder 7.8%, TPR33%, zinc stearate 2.2%, white carbon 10.2%, boric acid 1.2%, deca-BDE 9.5%, antioxidant 168 are 0.25%, mustard Sour acid amides 3.3%, organic siliconresin 14.05%.
Embodiment 2
As shown in Fig. 2 nanometer Rh- graphene combination electrodes are prepared by following steps,
Step 1：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, is stirred, control Reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 is slow into solution Sodium nitrate and potassium permanganate are added, stirs 10min；Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid：Deionized water Volume ratio 1:0.2 adds deionized water into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionization water body Product ratio 1:0.5 adds deionized water, stops reaction, according to graphite powder：Hydrogen peroxide mol ratio 1:0.2 adds 5% pair into solution Oxygen water, is centrifuged while hot, and respectively with appropriate 5% watery hydrochloric acid and distillation water washing, graphene oxide is made；
Step 2：Weigh a Rh（Ac）3, proper amount of methanol is taken as solvent, stirring at normal temperature dissolving, under condition of ice bath, According to rhodium acetate：Lithium hydroxide mol ratio 1:1.2 add LiOHH into solution2O methanol solution, 0 DEG C of controlling reaction temperature 8h is stirred, into solution according to rhodium acetate：N-hexane mol ratio 1:20 add n-hexane into solution, continue to stir 1h, filter, Precipitation is washed 3 times with distilled water and absolute methanol respectively, and product is scattered in ethanol, and it is 13.7mg/mL's to be configured to concentration Rh（OH）3Alcohol dispersion liquid；
Step 3：Weigh a graphene oxide to be scattered in ultrasonic wave in appropriate absolute ethyl alcohol, according to graphite oxide Alkene：Rhodium hydroxide：Urea mol ratio 1:1:0.5 adds the alcohol dispersion liquid that concentration is 13.7mg/mL rhodium hydroxides into solution With 5mol/L urea-ethanol solution, after 30min is stirred at room temperature, solution is transferred in reactor, is passed through argon gas as protection Hermetic seal, 160 DEG C react 24h, stop reaction, after product is filtered, with distillation water washing, then vacuum be 0.98 bar Freezed under part, then product is put into reactor, be passed through after argon gas is used as protection hermetic seal and heated under conditions of 300 DEG C 5.5h, obtain a nanometer Rh- graphene combination electrodes.
Embodiment 3
As shown in figure 3, nano Co2SnO4Polysulfonate acid naphthalene electrode is prepared by following steps,
Step 1：Weigh a SnCl4, appropriate amount of deionized water is taken as solvent, stirring and dissolving, according to stannic chloride：Chlorination Cobalt mol ratio 1:2 add CoCl into solution2, according to stannic chloride：Sodium hydroxide mol ratio 1:10 add NaOH's into solution The aqueous solution, stirring at normal temperature 10min, solution is placed in reactor, is passed through nitrogen：Oxygen 15:1 is passed through the mixing of nitrogen and oxygen Gas, sealing, reacts 30h under conditions of 240 DEG C, naturally cools to room temperature, washed respectively with deionized water and absolute ethyl alcohol, Freezed under conditions of being 0.98 in vacuum, obtain Co2SnO4Powder；
Step 2：Weigh a Co2SnO4Powder, by cobaltous stannate：Hydrochloric acid mol ratio 1:15 add 2mol/L hydrochloric acid solution As solvent, stirring and dissolving, according to cobaltous stannate：Sulfonic acid naphthalene：Potassium peroxydisulfate mol ratio 1:20：5 into solution add sulfonic acid naphthalene and Potassium peroxydisulfate, after ultrasonic wave disperses 30min, 5min is reacted under power 2000W microwave conditions, filtered, take filter residue respectively with steaming Distilled water and absolute ethyl alcohol washing filtrate under conditions of vacuum is 0.98, air drying 24h, obtain nanometer in neutrality Co2SnO4Polysulfonate acid naphthalene.
Embodiment 4
Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymers are prepared by following steps,
Step 1：Weigh a 1,2- dicyanos -1,2- two（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene, take appropriate N-amyl alcohol dissolves as stirring solvent, according to 1,2- dicyanos -1,2- bis-（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene：Vinegar Sour chromium mol ratio 1:2 add hexaaquochromium triacetate into solution, add appropriate DBU catalyst, and heating reflux reaction 20h is natural Normal temperature is cooled to, is steamed solvent by Rotary Evaporators, obtains Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin polymer；
Step 2：A Cr- di-thiofuran ethylenes base tetraazatetradecane porphyrin polymer is weighed, takes q. s. methylene chloride to make solvent, Ultrasonic wave disperses 30min, under the pressure of 5 atmospheric pressure, is put into reactor and heats 5h under conditions of 150 DEG C, naturally cold But to normal temperature, filtering, it is washed with deionized, under conditions of vacuum is 0.98, air drying 24h, obtains Cr- Dithiophenes Vinyl tetraazatetradecane porphyrin two dimension conjugated polymer.
Embodiment 5
Oligomeric cagelike silsesquioxane-graphene is prepared by following steps,
Step 1：A gamma-aminopropyl-triethoxy-silane is weighed, takes appropriate absolute ethyl alcohol to stir as solvent, According to gamma-aminopropyl-triethoxy-silane：Phenyl triethoxysilane mol ratio 1:1 adds phenyltriethoxy silane into solution Alkane, after stirring, according to gamma-aminopropyl-triethoxy-silane：Tetraethyl ammonium hydroxide mol ratio 1:1.2 add into solution Tetraethyl ammonium hydroxide, heating reflux reaction 48h, naturally cools to normal temperature, steams solvent by Rotary Evaporators, obtains stone Grey milky product, freezed with the mixed solution washed product of tetrahydrofuran and methanol, under vacuum condition and obtain diamine POSS；
Step 2：A graphite powder is weighed, the appropriate concentrated sulfuric acid is added under conditions of ice bath as solvent, is stirred, control Reaction temperature is less than under conditions of 20 DEG C, according to graphite powder：Sodium nitrate：Potassium permanganate mass ratio 1:0.5:3 is slow into solution Sodium nitrate and potassium permanganate are added, stirs 10min；Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid：Deionized water Volume ratio 1:0.2 adds deionized water into solution, is warming up to 98 DEG C, 30min is stirred, according still further to the concentrated sulfuric acid：Deionization water body Product ratio 1:0.5 adds deionized water, stops reaction, according to graphite powder：Hydrogen peroxide mol ratio 1:0.2 adds 5% pair into solution Oxygen water, is centrifuged while hot, and respectively with appropriate 5% watery hydrochloric acid and distillation water washing, graphene oxide is made；
Step 3：Weigh a graphene oxide to be scattered in ultrasonic wave in appropriate absolute ethyl alcohol, after stirring, press According to graphene oxide：Diamine POSS mol ratios 1:12 add diamine POSS into solution, according to graphene oxide：Dichloro two Luxuriant titanium mol ratio 1:0.5 adds cyclopentadienyl titanium dichloride into solution, and after 30min is stirred at room temperature, solution is transferred in reactor, leads to Enter argon gas as protection hermetic seal, react 36h at 210 DEG C, stop reaction, after product is filtered, with distillation water washing, then true Reciprocal of duty cycle freezes under conditions of being 0.98, obtains oligomeric cagelike silsesquioxane-graphene.
Embodiment 6
As shown in figure 4, polymer-LiClO4-Li4Ti5O12Composite electrolyte is prepared by following steps,
Step 1：A styrene is weighed, takes appropriate hexamethylene as solvent, stirring and dissolving, according to styrene：The tert-butyl group Lithium mol ratio 1:1.2 add tert-butyl lithium into solution, after stirring, are put into reactor, are heated to 80 DEG C, react 1h, 20 DEG C are cooled to after reaction, according to styrene：Vinylpyrrolidone mol ratio 1:1 adds vinylpyrrolidone into solution, stirs Mix and nitrogen is passed through in uniformly backward reactor as protection gas, after being warming up to 240 DEG C of reaction 3h, 20 DEG C are cooled to, according still further to second Alkene pyrrolidone：Styrene mol ratio 1:1 adds styrene into solution, and nitrogen conduct is passed through in the backward reactor that stirs Gas is protected, 240 DEG C of reaction 3h is warming up to, adds absolute methanol terminating reaction, solution is poured into absolute ethyl alcohol and precipitated, filter Afterwards, dried under vacuum condition, polystyrene-ethylene pyrrolidones-styrene triblock copolymer is made；
Step 2：A LiOH is weighed, according to lithium hydroxide：Titanium dioxide mol ratio 1:1 by lithium hydroxide solid and two Titanium oxide solid is well mixed, and is placed in Muffle furnace and is warming up to 800 DEG C of progress high temperature solid state reactions, naturally cold completely after reaction But take out, ball milling sub-sieve obtains Li4Ti5O12Nano-particle；
Step 3：A polystyrene-ethylene pyrrolidones-styrene triblock copolymer is weighed, takes appropriate acetonitrile to make For solvent, according to polystyrene-ethylene pyrrolidones-styrene triblock copolymer after stirring：LiClO4Mol ratio 20: 1 adds LiClO into solution4, according to LiClO after stirring4：Li4Ti5O12Mol ratio 1:1 adds Li into solution4Ti5O12 Nano-particle, stirring obtain white viscous liquid, mucus are poured into Teflon mould, freeze, obtain under vacuum condition Polymer-LiClO4-Li4Ti5O12Composite electrolyte.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (6)

  1. A kind of 1. battery of electrode overlay film, it is characterised in that：Including located at battery case（6）Internal positive plate（1）And negative pole Piece（2）, the positive plate（1）With negative plate（2）Between be provided with barrier film（5）；The positive plate（1）With barrier film（5）Between It is sequentially provided with positive pole overlay film（7）With anode catalytic net（3）, the positive pole overlay film（7）It is overlying on positive plate（1）Surface, it is described just Pole catalysis net（3）It is overlying on barrier film（5）Surface；The barrier film（5）With negative plate（2）Between be sequentially provided with negative pole catalysis net （4）With negative pole overlay film（8）, the negative pole catalysis net（4）It is overlying on barrier film（5）Surface, the negative pole overlay film（8）It is overlying on negative pole Piece（2）Surface；The positive plate（1）For nanometer Rh- graphene combination electrodes；The negative plate（2）For nano Co2SnO4It is poly- Sulfonic acid naphthalene electrode；The positive pole overlay film（7）For cell nafion proton membrane, the negative pole overlay film（8）For silica, the positive pole Overlay film（7）Thickness be 300nm, the negative pole overlay film（8）Thickness 300nm.
  2. A kind of 2. battery of electrode overlay film as claimed in claim 1, it is characterised in that：The positive plate（1）Thickness be 40 μ m；The negative plate（2）Thickness be 50 μm；The positive plate（1）Specific capacitance of being discharged when electric current is 1A/g is 576.3F/g, The negative plate（2）Specific capacitance of being discharged when electric current is 1A/g is 817.6F/g.
  3. A kind of 3. battery of electrode overlay film as claimed in claim 1 or 2, it is characterised in that：The anode catalytic net（3）Thickness Spend for 10 μm, the anode catalytic net（3）Anode catalyst is loaded with, the anode catalyst is Cr- di-thiofuran ethylenes base four Aza porphyrin two dimension conjugated polymer, the anode catalytic net（3）The bearing capacity of upper anode catalyst is 0.38mg/cm2；It is described Negative pole catalysis net（4）Thickness be 10 μm, the negative pole catalysis net（4）Cathode catalyst is loaded with, the cathode catalyst is Oligomeric cagelike silsesquioxane-graphene, the negative pole catalysis net（4）The bearing capacity of upper cathode catalyst is 0.71mg/cm2。
  4. A kind of 4. battery of electrode overlay film as claimed in claim 3, it is characterised in that：The barrier film（5）For polymer- LiClO4-Li4Ti5O12Composite electrolyte, the polymer are polystyrene-ethylene pyrrolidones-styrene triblock copolymer Thing, the barrier film（5）Thickness be 40 μm.
  5. A kind of 5. battery of electrode overlay film as claimed in claim 4, it is characterised in that：The barrier film（5）Surface is covered with painting Coating, the coat are Kynoar-hexafluoropropene, and the thickness of the coat is 100nm.
  6. A kind of 6. battery of electrode overlay film as described in claim 4 or 5, it is characterised in that：The Cr- di-thiofuran ethylenes base four Aza porphyrin two dimension conjugated polymer is prepared by following steps,
    Step 1：Weigh a 1,2- dicyanos -1,2- two（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene, take appropriate positive penta Alcohol dissolves as stirring solvent, according to 1,2- dicyanos -1,2- bis-（2 ', 4 ', 5 '-trimethyl -3 '-thiophene）Ethene：Chromic acetate Mol ratio 1:2 add hexaaquochromium triacetate into solution, add appropriate DBU catalyst, heating reflux reaction 20h, natural cooling To normal temperature, solvent is steamed by Rotary Evaporators, obtains Cr- di-thiofuran ethylene base tetraazatetradecane porphyrin polymer；
    Step 2：A Cr- di-thiofuran ethylenes base tetraazatetradecane porphyrin polymer is weighed, takes q. s. methylene chloride to make solvent, ultrasound Wavelength-division dissipates 30min, under the pressure of 5 atmospheric pressure, is put into reactor and heats 5h under conditions of 150 DEG C, naturally cool to Normal temperature, filtering, is washed with deionized, and under conditions of vacuum is 0.98, air drying 24h, obtains Cr- di-thiofuran ethylenes Base tetraazatetradecane porphyrin two dimension conjugated polymer.
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