CN106450309B - A kind of preparation method of the aluminium ion battery of flexible - Google Patents
A kind of preparation method of the aluminium ion battery of flexible Download PDFInfo
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- CN106450309B CN106450309B CN201610845761.6A CN201610845761A CN106450309B CN 106450309 B CN106450309 B CN 106450309B CN 201610845761 A CN201610845761 A CN 201610845761A CN 106450309 B CN106450309 B CN 106450309B
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 121
- 239000004744 fabric Substances 0.000 claims abstract description 56
- 230000001112 coagulating effect Effects 0.000 claims abstract description 51
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical group 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- 241001122767 Theaceae Species 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- -1 graphite alkenes Chemical class 0.000 description 5
- 229940071870 hydroiodic acid Drugs 0.000 description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 210000000941 bile Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/054—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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of the aluminium ion battery of flexible.Graphene oxide or graphene oxide inorganic salts mixed liquor are first expressed into the inorganic salt solution coagulating bath of rotation by this method in the spinning equipment of certain diameter, then the graphene oxide cloth collected the short fibre in coagulating bath with strainer filtering and be overlapped to form staple fiber is placed in reduction in reducing environment and obtains graphene cloth；Then resulting graphene cloth positive electrode and diaphragm, cathode, electrolyte and battery case assemble, and obtain the aluminium ion battery using graphene cloth as positive electrode.The present invention is environmentally protective, at low cost, is suitble to continuous controllable large-scale industrial production.Under the premise of guaranteeing the higher energy density of aluminium ion battery, power density and cycle life, the flexible bending performance of battery is realized, the wearable energy storage device field suitable for high security.
Description
Technical field
The present invention relates to using the graphene cloth with flexible as the preparation side of the aluminium ion battery of positive electrode
Method.
Background technique
With the development of science and technology the electronic equipments such as smart phone, Intelligent bracelet emerge one after another, its power-supply battery is also mentioned
New requirement is gone out.Lithium ion battery is as new secondary battery, increasingly because of the advantages that its self discharge is small, specific discharge capacity is high
Favored.However, the natural abundance of elemental lithium is low, the defects of inflammable in air, easy formation dendrite limited to it is daily just
Application in portable device.The negative electrode material of aluminium ion battery is aluminum metal or alloy, and aluminium element is in nature rich reserves
And it can be stabilized in air.The above advantage make aluminium ion battery in flexible portable's electronic equipment have widely answer
Use prospect.
Graphene was found so far from 2004, due to its superior conductive, heating conduction and high intensity, Large ratio surface
Product, so that it is widely used in fields such as battery, capacitor, transistor, nanofiltration membranes.But pure graphite alkenes anode
Material is not applied also in aluminium ion field of batteries, especially flexible aluminium ion battery.The common positive material of current aluminium ion battery
Material includes: pyrolytic graphite, nickel sulfide graphene composite material etc..But the preparation of these positive electrodes is complicated, and it is at high cost, do not have
Characteristic is mass produced and does not have flexible, is unable to satisfy the requirement of wearing portable equipment.
Summary of the invention
The purpose of the present invention is to propose to a kind of flexible and the preparation methods of the aluminium ion battery of high-energy density, are
Novel aluminium ion cell positive material pattern provides new thinking.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of preparation of the aluminium ion battery of flexible
Method includes the following steps:
1) it adds graphene oxide into solvent, ultrasonic disperse handles to obtain graphene oxide concentration to be 0.1mgmL-1-20mg·mL-1Graphene oxide solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30-500 micron diameters；
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber in coagulating bath is overlapped to form graphite oxide on strainer
Graphene oxide, is then arranged in reducing environment by alkene cloth, and reduction obtains the graphene cloth of high conductivity；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.
A kind of preparation method of the aluminium ion battery of flexible, includes the following steps:
1) graphene oxide and inorganic salts are added in solvent, ultrasonic disperse handle to obtain graphene oxide concentration be
0.1mg·mL-1-20mg·mL-1Graphene oxide solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30-500 micron diameters；
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber in coagulating bath is overlapped to form graphite oxide on strainer
Graphene oxide, is then arranged in reducing environment by alkene cloth, and reduction obtains the graphene cloth of high conductivity；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.
Further, the concentration of the inorganic salts be 1~5mg/mL, by ammonium hydrogen carbonate, ammonium carbonate, ammonium chloride one kind or
The a variety of mixing compositions in any proportion of person
Further, the solvent of the step 1) is mainly by deionized water, N-Methyl pyrrolidone, N, N- dimethyl formyl
Amine, n,N-dimethylacetamide, acetone, butanone, pyridine, dimethyl sulfoxide one or more according to arbitrary proportion mixing group
At.
Further, in ethyl acetate or inorganic salt solution, the inorganic salt solution, solute is inorganic for coagulating bath
Salt, concentration are 1wt% -10wt%, and inorganic salts are selected from calcium chloride, magnesium chloride, ammonium chloride, sodium hydroxide, potassium hydroxide；Solvent
The water and alcohol mixed solution for ethyl alcohol or arbitrarily matched；The revolving speed of coagulating bath is in 200-1200RPM.
Further, it is the hydrazine hydrate solution of 1%-40%, quality that the reducing environment of the step 3), which is selected from mass fraction,
Phenylhydrazine aqueous solution that ascorbic acid sodium water solution that score is 1%-40%, mass fraction are 1%-40%, mass fraction are
Tea polyphenols aqueous solution that hydrobromic acid aqueous solution, the mass fraction of 1%-40% is 1%-40%, mass fraction are 1%-40%'s
The hydroiodic acid water that sodium thiosulfate solution that aqueous solution of urea, mass fraction are 1%-20%, mass fraction are 1%-40%
Solution, mass fraction are the aqueous acetic acid of 1%-40%, 200-3000 DEG C of thermal reduction.
Further, with a thickness of 50 microns to 2 millimeters, conductivity is greater than graphene cloth described in the step 3)
104S/m。
Further, the cathode of the step 4) is aluminium alloy or aluminum metal；Diaphragm be glass carbon fiber, PP diaphragm or PE every
Film；Electrolyte is selected from imidazoles chloroaluminate ionic liquid, quaternary ammonium salt chloroaluminate ionic liquid.
The present invention has the advantages that aluminum cell of the invention is melted certainly using graphene staple fiber compared with prior art
The carbon felt-like material being formed by overlapping is closed, compared to common membrane material or pyrolyzing graphite material, between fiber and fiber
With many gaps, be conducive to the transmission of high viscosity low temperature molten salt electrolysis liquid, provide excellent high rate performance, charge and discharge times
Rate can reach 50C；In single fiber, graphene sheet layer be again Close stack together, it is ensured that the mass density of battery
It is larger with bulk density.On the other hand, due to the high porosity between fiber, be conducive to aluminum ions absorption, provide class
The fast charging and discharging characteristic and high power density of capacitor；Due to the graphene sheet layer of fibrous inside high-specific surface area and its
Close stack provides active reaction sites for aluminum ions insertion, provides the high-energy density of class battery.Meanwhile anode
Material is formed by overlapping by graphene staple fiber from fusion, and interfibrous merging point provides excellent mechanical property, so that it has
Good bending property and certain elasticity, material can any bending folds.Based on the above feature, what the present invention was prepared
There is aluminium ion battery high-energy density 60Wh/Kg to take into account high power density 30W/Kg, the cycle life up to 10000 times, 50C
Fast charging and discharging performance, the advantages of taking into account supercapacitor and battery and flexible bending performance.Its excellent electric property
The aluminium ion battery for mechanical property being prepared by this method has prospect in wearable bile devices.
The preparation method that the present invention uses, compared to using materials such as pyrolytic graphites, technique is environmentally protective, at low cost,
Macroscopic form is controllable, can be directly applied for current existing battery industry assembling process.
Detailed description of the invention
Fig. 1 is the flexible aluminium ion battery schematic diagram of present device；
Fig. 2 is cycle performance curve of the flexible aluminium ion battery of present device under the conditions of 50C constant current charge-discharge；
Fig. 3 is the scanning electron microscope (SEM) photograph of the graphene measuring fiber in example 1 through hydrazine hydrate reduction；
Fig. 4 a is the surface sweeping electron microscope of the graphene measuring fiber in example 2 through heat-treating；Fig. 4 b is in example 2 through heat-treating
Graphene cloth section surface sweeping electron microscope.
Specific embodiment
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art's content according to the present invention is made
Nonessential change and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1:
1) graphene oxide of 1 parts by weight is added in the deionized water of 1000 parts by weight, in the ultra sonic bath of 20Hz
Processing 1 hour, obtaining concentration is 1mgmL-1Graphene oxide dispersion；
2) graphene oxide dispersion is expressed into the coagulating bath of rotation in 100 microns of diameter of spinneret, is solidified
Bath formula is: the volume ratio of ethyl alcohol and water is 3:1, and the mass fraction of calcium chloride is 5%.Coagulating bath revolving speed is 1000RPM；
3) collect coagulating bath with strainer filtering, the graphene oxide fiber in coagulating bath (fibre length is at 8~10 centimetres)
Graphene oxide cloth is overlapped to form on strainer.It is lyophilized after graphene oxide arrangement is dried 2 hours at room temperature, then will be after freeze-drying
Graphene oxide be arranged in 500mL closed container, bottom instills the hydrazine hydrate aqueous solution that 5mL concentration is 40wt%, and in 80
It is restored 8 hours at DEG C, obtains the graphene cloth of high conductivity；
4) resulting graphene cloth is cut into the square of 10cm*10cm as anode, is born with fibreglass diaphragm, aluminium foil
Pole pole piece, AlCl3/ [EMIm] Cl ionic liquid and the assembling of aluminum plastic film soft-package battery shell, obtain using graphene cloth as positive electrode
Flexible aluminium ion battery.
It is as shown in Figure 4 to the morphology characterization of the graphene cloth of such method preparation.Show that graphene fiber internal voids are equal
It is even, be conducive to adsorb aluminium ion, enhance capacitive properties, improves charge-discharge velocity.Its conductivity is about 200S/cm.
The coagulating bath of the embodiment is water phase, and the fiber obtained it can be seen from scanning electron microscope (SEM) photograph is more loose, porosity
It is higher.Its chemical property is as shown in Figure 2 a.Due to porosity height, the ability of adsorption activity substance is strong, so capacitive properties
Proportion wants high compared with example 2.Specific capacity when 5C is about 110mAh/g, and specific capacity when 50C is about 90mAh/g, but steady
Determine cycle life and there was only 3000 circles.This is because the graphene fiber cloth porosity of water phase is higher, the contact area with electrolyte
Bigger, the active site that can be provided is more, so specific capacity improves.
Embodiment 2:
1) graphene oxide of 5 parts by weight is added in the n,N-Dimethylformamide of 1000 parts by weight, 50Hz's
It is handled 0.5 hour in ultra sonic bath, obtains concentration for 5mgmL-1Graphene oxide dispersion；
2) graphene oxide dispersion is expressed into the coagulating bath of rotation in 130 microns of diameter of spinneret, is solidified
Bath is ethyl acetate solution.Coagulating bath revolving speed is 700RPM；
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber (about 10 centimetres of fibre length) in coagulating bath is being filtered
It is overlapped to form graphene oxide cloth on the net.After graphene oxide arrangement is dried 5 hours at room temperature, then it is placed in 60 DEG C of oven dryings
Remove solvent.Graphene oxide after drying is arranged in nitrogen atmosphere, 2800 DEG C are heated in graphitizing furnace and keeps one
Hour, obtain the graphene cloth of high conductivity；
4) resulting graphene cloth is cut into the square of 10cm*10cm as anode, is born with fibreglass diaphragm, aluminium foil
Pole pole piece, AlCl3/ [EMIm] Cl ionic liquid and the assembling of aluminum plastic film soft-package battery shell, obtain using graphene cloth as positive electrode
Flexible aluminium ion battery.
It is as shown in Figure 4 to the morphology characterization of the graphene cloth of such method preparation.Show to heat-treat fibrous inside graphene
Lamella stacks densification, is conducive to aluminum ions insertion and deintercalation, improves energy density.Its conductivity is about 500S/cm.
The coagulating bath of the embodiment is organic phase, and the fiber obtained it can be seen from scanning electron microscope (SEM) photograph is comparatively dense, graphite
Alkene lamella stacks closely, and porosity is smaller compared with embodiment 1.Its chemical property is as shown in Figure 2 b.Since porosity is low, class electricity
Pond property proportion is higher, and class capacitive properties accounting example is lower.Specific capacity when 5C is about 95mAh/g, specific capacity when 50C
About 75mAh/g.Stablize cycle life up to 10000 circles.
Embodiment 3:
1) by the graphene oxide of 1 parts by weight, the ammonium hydrogen carbonate inorganic salts of a parts by weight are added to going for 1000 parts by weight
It in ionized water, is handled 1 hour in the ultra sonic bath of 20Hz, obtains concentration for 1mgmL-1Graphene oxide dispersion；
2) graphene oxide dispersion is expressed into the coagulating bath of rotation in 150 microns of diameter of spinneret, is solidified
Bath formula is: the volume ratio of ethyl alcohol and water is 3:1, and the mass fraction of calcium chloride is 5%.Coagulating bath revolving speed is 1000RPM；
3) collect coagulating bath with strainer filtering, the graphene oxide fiber in coagulating bath (fibre length is at 8~10 centimetres)
Graphene oxide cloth is overlapped to form on strainer.It is lyophilized after graphene oxide arrangement is dried 2 hours at room temperature, then will be after freeze-drying
Graphene oxide be arranged in 500mL closed container, it is 40wt% hydrazine hydrate aqueous solution that bottom, which instills 5mL concentration, and in 80 DEG C
Lower reduction 8 hours, obtains the graphene cloth of high conductivity；
4) resulting graphene cloth is cut into the square of 10cm*10cm as anode, is born with fibreglass diaphragm, aluminium foil
Pole pole piece, AlCl3/ [EMIm] Cl ionic liquid and the assembling of aluminum plastic film soft-package battery shell, obtain using graphene cloth as positive electrode
Flexible aluminium ion battery.
It is as shown in Figure 4 to the morphology characterization of the graphene cloth of such method preparation.Show that hydrazine hydrate fibrous inside gap is equal
It is even, be conducive to adsorb aluminium ion, enhance capacitive properties, improves charge-discharge velocity.Its conductivity is about 200S/cm.
Embodiment 4
A kind of preparation method of the aluminium ion battery of flexible, includes the following steps:
1) it adds graphene oxide into deionized water, ultrasonic disperse handles to obtain concentration to be 0.1mgmL-1Oxidation
Graphene solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30 micron diameters；Coagulating bath is
Ethyl acetate；The revolving speed of coagulating bath is in 200RPM.
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber (fibre length is at 2-4 centimetres) in coagulating bath exists
Graphene oxide cloth is overlapped to form on strainer, then by graphene oxide hydroiodic acid solution reduction, reduction obtains high conductivity
Graphene cloth；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.After tested, there is preferable cycle life and charge-discharge performance.
Embodiment 5
A kind of preparation method of the aluminium ion battery of flexible, includes the following steps:
1) it adds graphene oxide into N-Methyl pyrrolidone, ultrasonic disperse handles to obtain concentration to be 20mgmL-1
Graphene oxide solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 500 micron diameters；Coagulating bath
For ethyl acetate；The revolving speed of coagulating bath is in 1200RPM.
3) collect coagulating bath with strainer filtering, the graphene oxide fiber in coagulating bath (fibre length is at 8-10 centimetres)
Graphene oxide cloth is overlapped to form on strainer, after by graphene oxide hydroiodic acid solution reduction, reduction obtains high conductivity
Graphene cloth；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.After tested, there is preferable cycle life and charge-discharge performance.
Embodiment 6
A kind of preparation method of the aluminium ion battery of flexible, includes the following steps:
1) graphene oxide and ammonium hydrogen carbonate are added in dimethyl sulfoxide, ultrasonic disperse handle to obtain concentration be
0.1mg·mL-1Graphene oxide solution；The concentration of ammonium hydrogen carbonate is 1~5mg/mL；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30 micron diameters；Coagulating bath is
Concentration is 8wt% aqueous ammonium chloride solution；The revolving speed of coagulating bath is in 200-1200RPM.
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber (fibre length is at 2-4 centimetres) in coagulating bath exists
It is overlapped to form graphene oxide hydroiodic acid solution reduction on strainer after graphene oxide cloth, reduction obtains the graphite of high conductivity
Alkene cloth；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.After tested, there is preferable cycle life and charge-discharge performance.
Embodiment 7
A kind of preparation method of the aluminium ion battery of flexible, includes the following steps:
1) graphene oxide and ammonium chloride are add to deionized water, ultrasonic disperse handles to obtain concentration to be 0.1mg
mL-1-20mg·mL-1Graphene oxide solution；The concentration of the ammonium chloride is 1~5mg/mL.
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 500 micron diameters；Coagulating bath
For ethyl acetate；
3) collect coagulating bath with strainer filtering, the graphene oxide fiber in coagulating bath (fibre length is at 8-10 centimetres)
Graphene oxide cloth is overlapped to form on strainer, after by graphene oxide hydroiodic acid solution reduction, reduction obtains high conductivity
Graphene cloth；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphite with diaphragm, cathode, electrolyte and battery case
Alkene cloth is the flexible aluminium ion battery of positive electrode.After tested, there is preferable cycle life and charge-discharge performance.
Claims (6)
1. a kind of preparation method of the aluminium ion battery of flexible, which comprises the steps of:
1) it adds graphene oxide into solvent, ultrasonic disperse handles to obtain graphene oxide concentration to be 0.1mg mL-1-
20mg•mL-1Graphene oxide solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30-500 micron diameters；
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber in coagulating bath is overlapped to form graphene oxide on strainer
Then graphene oxide is arranged in reducing environment by cloth, reduction obtains the graphene cloth of high conductivity；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphene cloth with diaphragm, cathode, electrolyte and battery case
For the flexible aluminium ion battery of positive electrode；
The reducing environment of the step 3) is selected from the hydrazine hydrate solution that mass fraction is 1%-40%, mass fraction is the anti-of 1%-40%
Hydrobromic acid aqueous solution that phenylhydrazine aqueous solution that bad hematic acid sodium water solution, mass fraction are 1%-40%, mass fraction are 1%-40%, matter
Measure score be 1%-40% tea polyphenols aqueous solution, mass fraction be 1%-40% aqueous solution of urea, mass fraction be 1%-20%'s
Aqueous acetic acid that hydriodic acid aqueous solution that sodium thiosulfate solution, mass fraction are 1%-40%, mass fraction are 1%-40%,
200-3000 DEG C of thermal reduction.
2. a kind of preparation method of the aluminium ion battery of flexible, which comprises the steps of:
1) graphene oxide and inorganic salts are added in solvent, ultrasonic disperse handles to obtain graphene oxide concentration to be 0.1mg
mL-1-20mg•mL-1Graphene oxide solution；
2) by graphene oxide solution from the coagulating bath for being expressed into rotation in the spinneret of 30-500 micron diameters；
3) coagulating bath is collected with strainer filtering, the graphene oxide fiber in coagulating bath is overlapped to form graphene oxide on strainer
Then graphene oxide is arranged in reducing environment by cloth, reduction obtains the graphene cloth of high conductivity；
4) it using resulting graphene cloth as anode, assembles, is obtained with graphene cloth with diaphragm, cathode, electrolyte and battery case
For the flexible aluminium ion battery of positive electrode；
In the step 1), the concentration of inorganic salts is 1 ~ 5mg/mL, by ammonium hydrogen carbonate, ammonium carbonate, ammonium chloride it is a kind of or more
Mixing forms kind in any proportion；
The reducing environment of the step 3) is selected from the hydrazine hydrate solution that mass fraction is 1%-40%, mass fraction is the anti-of 1%-40%
Hydrobromic acid aqueous solution that phenylhydrazine aqueous solution that bad hematic acid sodium water solution, mass fraction are 1%-40%, mass fraction are 1%-40%, matter
Measure score be 1%-40% tea polyphenols aqueous solution, mass fraction be 1%-40% aqueous solution of urea, mass fraction be 1%-20%'s
Aqueous acetic acid that hydriodic acid aqueous solution that sodium thiosulfate solution, mass fraction are 1%-40%, mass fraction are 1%-40%,
200-3000 DEG C of thermal reduction.
3. the preparation method of the aluminium ion battery of flexible as claimed in claim 1 or 2, it is characterised in that: the step
Rapid solvent 1) is by deionized water, N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, fourth
Ketone, pyridine, the one or more kinds of of dimethyl sulfoxide mix composition according to arbitrary proportion.
4. the preparation method of the aluminium ion battery of the flexible as described in claim 1, it is characterised in that: coagulating bath choosing
From ethyl acetate or inorganic salt solution, in the inorganic salt solution, solute is inorganic salts, and concentration is 1wt% -10wt%, inorganic salts
Selected from calcium chloride, magnesium chloride, ammonium chloride, sodium hydroxide, potassium hydroxide；Solvent is that ethyl alcohol or the water arbitrarily matched are mixed with ethyl alcohol
Solution；The revolving speed of coagulating bath is in 200-1200 RPM.
5. the preparation method of the aluminium ion battery of the flexible as described in claim 1 or 2, it is characterised in that: described
For graphene cloth described in step 3) with a thickness of 50 microns to 2 millimeters, conductivity is greater than 104S/m。
6. the preparation method of the aluminium ion battery of flexible as claimed in claim 1 or 2, it is characterised in that: the step
Rapid cathode 4) is aluminium alloy or aluminum metal；Diaphragm is glass carbon fiber, PP diaphragm or PE diaphragm；Electrolyte is imidazoles chlorine aluminic acid
Ionic liquid or quaternary ammonium salt chloroaluminate ionic liquid.
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| CN107706007A (en) * | 2017-10-13 | 2018-02-16 | 北京航空航天大学 | A kind of aquo-lithium ion ultracapacitor based on graphene and organic molecule |
| CN109830682B (en) * | 2019-02-01 | 2021-04-27 | 东北大学 | Preparation method and application method of positive electrode material for high-capacity aluminum battery |
| CN110299508B (en) * | 2019-06-24 | 2022-06-28 | 盐城师范学院 | 3D graphene based carbon positive electrode full battery and preparation method thereof |
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| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
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-
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- 2016-09-23 CN CN201610845761.6A patent/CN106450309B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104993130A (en) * | 2015-05-25 | 2015-10-21 | 石嘴山市天和创润新材料科技有限公司 | Non-aqueous solution aluminum ion secondary battery and preparation method thereof |
| CN105529463A (en) * | 2015-12-09 | 2016-04-27 | 江苏科技大学 | High cycle-performance secondary aluminium ion battery and preparation method |
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