CN105261784B - A kind of aluminum secondary battery - Google Patents
A kind of aluminum secondary battery Download PDFInfo
- Publication number
- CN105261784B CN105261784B CN201410336027.8A CN201410336027A CN105261784B CN 105261784 B CN105261784 B CN 105261784B CN 201410336027 A CN201410336027 A CN 201410336027A CN 105261784 B CN105261784 B CN 105261784B
- Authority
- CN
- China
- Prior art keywords
- barium oxide
- secondary battery
- collector
- aluminum secondary
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 101
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 220
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 47
- 239000006260 foam Substances 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 230000008021 deposition Effects 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 8
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 8
- 239000011152 fibreglass Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 6
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 10
- 230000001965 increasing effect Effects 0.000 abstract description 7
- 239000006258 conductive agent Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 description 35
- 238000000151 deposition Methods 0.000 description 32
- 239000007788 liquid Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 229910001935 vanadium oxide Inorganic materials 0.000 description 14
- 239000002608 ionic liquid Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- -1 imidazolium halide salt Chemical class 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOLFMOZUQSZTML-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;chloride Chemical compound [Cl-].CCCN1C=C[N+](C)=C1 JOLFMOZUQSZTML-UHFFFAOYSA-M 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000006713 insertion reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HDXFBBSZRMZTFF-UHFFFAOYSA-N 1-methyl-3-pentyl-2h-imidazole Chemical compound CCCCCN1CN(C)C=C1 HDXFBBSZRMZTFF-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of aluminum secondary batteries, the aluminum secondary battery includes anode, cathode, electrolyte and diaphragm, the anode is the combination for growing barium oxide and collector on a current collector, the preparation method of the anode obtains vanadium ion solution the following steps are included: (1) dissolves vfanadium compound；(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, reaction product is cleaned and is dried in vacuo after reaction, obtain combination.The anode of aluminum secondary battery of the invention, the barium oxide growth of nanoparticle structure is on a current collector, so that not only having electrical contact well between the two, addition conductive agent and binder are not needed, and it is capable of increasing the surface area of barium oxide electrode material, the contact area of electrode material and electrolyte is improved, meanwhile, aluminum secondary battery of the invention specific discharge capacity with higher and excellent stable circulation performance.
Description
Technical field
The present invention relates to aluminum secondary battery fields, and in particular, to a kind of aluminum secondary battery.
Background technique
Advanced high-energy density secondary battery is effective to the development of next-generation electric car and renewable energy power generation
Using being vital.In recent years, the novel green secondary cell research based on new system, new material, new technology is constantly deep
Change, by constructing for light element polyelectron reaction system, is expected that secondary cell is made to obtain energy more higher than conventional single electron system
Metric density.Aluminium is the most abundant metallic element of content on the earth, it has many advantages, such as light weight, pollution-free, cheap, because of it
Three electron transfer reactions can occur, theoretical electrochemistry specific capacity reaches 2980mAh/g, is only second to lithium in all metallic elements
(3870mAh/g)。
Since aluminium is a kind of very active metal, standard electrode potential is -1.68V, is lower than standard hydrogen-evolution overpotential, because
This aluminium ion is difficult to restore in aqueous solution, can generate strong evolving hydrogen reaction.So the electrolytic deposition and aluminium in aluminium are secondary
In the research and application of battery, non-aqueous solution electrolysis plastidome is generallyd use.And aluminium is easy film forming in neutral and organic electrolyte
And be passivated, lead to that electrode potential is substantially less than theoretical value and voltage behavior obviously lags, therefore aluminium is never successfully applied
In electrochemical energy storage and switch technology.In the 1970s, it is found that electrochemistry can occur in molten salt electrolyte for aluminium
Deposition, then using the aluminium electrode preparation research electrochemical behavior of secondary molten salt battery.Compared with aqueous electrolyte, fused salt tool
There is the features such as conductivity is high, and decomposition potential is high, and polarizability is low, the high-temperature molten salt aluminum secondary battery constituted has good reversibility,
The features such as theoretical specific energy is big.But high-temperature molten salt battery needs high temperature or to environmental requirement harshness, higher cost and is difficult to safeguard,
Limit the development of aluminum secondary battery.
Ionic liquid at room temperature is the substance being made of ion being in a liquid state at a temperature of room temperature or near room temperature, generally by having
Machine cation and inorganic anion composition.It not only has very low vapour pressure, has good dissolution to organic matter, inorganic matter
Property, and thermal stability and good flame resistance, also there is good ionic conductivity, stable electrochemical window is expected to become one kind
Safe and efficient secondary cell electrolyte.So far, ionic liquid has been widely studied as lithium-ion battery electrolytes.
It is nearest the study found that aluminum chloride type ionic liquid can be good at being used in aluminum secondary battery as electrolyte, make room temperature aluminium
The exploitation of secondary cell is possibly realized with application.The electrolyte being related in reported aluminum secondary battery is mainly aluminum chloride type
Ionic liquid, including AlCl3/[EMIM]Cl、AlCl3/ [BMIM] Cl and AlCl3/ [BMIM] Br etc..Aluminum chloride type ionic liquid
The characteristics of be itself contain aluminium ion, and form with the ratio of aluminium chloride and imidazolium halide salt change and change, already exist
It is studied in the electrolytic deposition field of aluminium.Metallic aluminium can only be deposited from acid melt, because of AlCl4 -With high degree of symmetry
Tetrahedral structure, electrochemically stable, the electrodeposition efficiency of aluminium is low.And Al in acid melt2Cl7 -Due to the asymmetry of its structure
Property, electro-chemical activity is high, being capable of effectively electric deposition aluminum.But the Al in acid chlorization aluminium profiles ionic liquid2Cl7 -Can with it is common
Binder PVDF reaction, therefore the ionic liquid of the type should not be used in the battery constituted using PVDF as the electrode of binder.
Barium oxide is the typical embedded type compound with layer structure, because it is high with theoretical specific capacity, resource is rich
Rich, lower-price characteristic, becomes one of lithium ion battery electrode material of new generation.Recent studies have found that it is used as the secondary electricity of aluminium
The insertion reaction of aluminium, specific discharge capacity with higher can occur for pond positive electrode.Cornell University Jayaprakash et al. will
The barium oxide nano wire of hydro-thermal reaction synthesis is as positive electrode, by AlCl3With the molar ratio of [EMIm] Cl be 1.1:1 from
Sub- liquid constitutes secondary aluminium ion battery as electrolyte, using metallic aluminium as cathode.Constant current charge-discharge survey is carried out to battery
Examination, as a result, it has been found that, open-circuit voltage 1.8V, discharge voltage plateau is basically stable at 0.55V, and specific discharge capacity is within first week
305mAh/g.But when preparing anode electrode, barium oxide nano wire needs to add conductive agent, with binder mixed pulp
Coated on anode electrode can just be prepared on collector, on the one hand, the adhesive property and electric conductivity of binder are to be improved,
And the wellability of acid chlorization aluminium profiles il electrolyte is poor, it is incompatible with binder, be unfavorable for barium oxide nano wire with
Electrical contact between conducting base is also unfavorable for keeping the stability of anode electrode；On the other hand, the barium oxide nano wire
Conductivity is very low so that ion telescopiny slowly and only one layer of surface participations insertion reaction, be unfavorable for anode electrode and
Contact between electrolyte.
Summary of the invention
The purpose of the invention is to overcome acid chlorization aluminium profiles ionic liquid in the aluminum secondary battery of the prior art to be electrolysed
Liquid wellability is poor, incompatible with binder, the electrical contact being unfavorable between barium oxide nano wire and conducting base and vanadium oxygen
Compound nano wire conductivity is low, is unfavorable for the defect of the contact between anode electrode and electrolyte, and it is secondary to provide a kind of new aluminium
Battery all has in the aluminum secondary battery well between barium oxide and conducting base and between anode electrode and electrolyte
Electrical contact, and aluminum secondary battery specific discharge capacity with higher and excellent stable circulation performance.
The present inventor has been surprisingly found that under study for action, (leads in the collector with large scale tridimensional network
Electric matrix) on using hydro-thermal in-situ deposition barium oxide method (that is, allowing barium oxide directly to synthesize and being deposited on collector
On) anode (combination for growing barium oxide and collector on a current collector) for preparing aluminum secondary battery, it can not only
The channel for keeping collector netted is conducive to electrolyte and migrates and spread inside it, further increases vanadium oxide positive electrode material
Material with the utilization rate of contact and positive electrode between electrolyte, and as the barium oxide of active material with as collector
Conducting base between have well electrical contact, do not need to add any conductive agent and binder, and be able to maintain good
The stability of anode electrode.Meanwhile so that the aluminum secondary battery being assembled into specific discharge capacity with higher and excellent circulation
Stability.
Therefore, to achieve the goals above, the present invention provides a kind of aluminum secondary battery, the aluminum secondary battery includes just
Pole, cathode, electrolyte and diaphragm, the anode is the combination for growing barium oxide and collector on a current collector, described
Anode preparation method the following steps are included:
(1) vfanadium compound is dissolved, obtains vanadium ion solution；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, carry out reaction product after reaction
Cleaning and vacuum drying, obtain growing the combination of barium oxide and collector on a current collector.
Aluminum secondary battery of the invention specific discharge capacity with higher and excellent stable circulation performance.
When the present invention prepares anode, by first preparing vanadium ion solution, the method for then using hydro-thermal in-situ deposition, by vanadium
For solion heat resolve at the barium oxide nano particle and water of unformed shape, the nanoparticle structure made is grown in collection
On fluid, addition conductive agent and binder are not needed, that is, may make not only has electrical contact well between the two, is able to maintain
The stability of good anode electrode, and it is capable of increasing the surface area of vanadium oxide positive electrode materials, improve positive electrode and electricity
The contact area of liquid is solved, diffusion length needed for shortening aluminium ion and electronics, so as to improve the specific discharge capacity of battery, and
Improve its stable circulation performance.In a preferred embodiment of the invention, by the combination obtained after vacuum drying into
Row heat treatment (condition of heat treatment includes: that temperature is 300-600 DEG C, time 1-6h), so that barium oxide is by amorphous state knot
Structure turns to crystalline structure, is conducive to the raising of barium oxide crystallinity, can further increase the specific discharge capacity of battery and follow
Ring stability.Meanwhile hydro-thermal reaction is carried out in closed container, it carries out reaction under relatively high temperature and pressure, reacts
The viscosity of fast speed, hydrothermal solution is low compared with the viscosity under normal temperature and pressure, and the diffusion of reactive component is very fast, and crystal growth interface is attached
Close diffusion region is narrower, is more advantageous to the growth of crystal.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the XRD spectrum of barium oxide prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM picture before vanadium oxide positive electrode materials calcining prepared by the embodiment of the present invention 1.
Fig. 3 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 1.
Fig. 4 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 2.
Fig. 5 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 3.
Fig. 6 is the calcined SEM picture of vanadium oxide positive electrode materials prepared by the embodiment of the present invention 4.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of aluminum secondary battery, which includes anode, cathode, electrolyte and diaphragm,
In, anode is the combination for growing barium oxide and collector on a current collector, and the preparation method of the anode includes following
Step:
(1) vfanadium compound is dissolved, obtains vanadium ion solution；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, carry out reaction product after reaction
Cleaning and vacuum drying, obtain growing the combination of barium oxide and collector on a current collector.
In aluminum secondary battery of the invention, when preparing anode, in step (1), under preferable case, vfanadium compound is dissolved
Method includes: under stiring, the solution that can dissolve vfanadium compound to be added in vfanadium compound, and the time of stirring is 0.5-3h.
It will be understood by those skilled in the art that the solution that can dissolve vfanadium compound can if vfanadium compound can be dissolved in water
Think water；If vfanadium compound is not soluble in water, described can to dissolve the solution of vfanadium compound can be aqueous hydrogen peroxide solution, grass
Aqueous acid, aqueous hydrochloric acid solution or ammonia spirit.Therefore, the solution that can dissolve vfanadium compound can be water, aquae hydrogenii dioxidi
Solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia spirit.For aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution
Or there is no particular limitation for the concentration of ammonia spirit, as long as vfanadium compound can be dissolved, in order to preferably dissolve vanadium
Compound, under preferable case, the concentration of aqueous hydrogen peroxide solution is 15-30 weight %, and the concentration of oxalic acid aqueous solution is 5-12.5
Weight %, the concentration of aqueous hydrochloric acid solution are 15-37 weight %, and the concentration of ammonia spirit is 15-28 weight %.In vfanadium compound
Prepared energy can be added when can dissolve solution (in the case where being not water, such as the oxalic acid solution) of vfanadium compound in addition
The aqueous solution (such as oxalic acid aqueous solution) for enough dissolving vfanadium compound, can also be separately added into water and can dissolve the substance of vfanadium compound
(such as oxalic acid).
In aluminum secondary battery of the invention, when preparing anode, the present inventor has found under study for action, uses peroxidating
When aqueous solution of hydrogen dissolves vfanadium compound, the time of stirring has an impact to the deposition of barium oxide on collector, mixing time mistake
It is long, the deposition of barium oxide on collector can be reduced, this may be because with stirring progress, hydrogen peroxide light-exposed and
Having and is constantly catalytically decomposed in the presence of barium oxide, long agitation decomposes excessive hydrogen peroxide completely, and
The pervanadic acid of generation is unstable, will be slow resolve into vanadic anhydride and oxygen at room temperature, eventually leads to vanadic anhydride analysis
Out, vanadium ion solution concentration reduces, to reduce barium oxide in the deposition of collection liquid surface.In the case of it is therefore preferable that, stir
The time mixed is 0.5-3h.
In aluminum secondary battery of the invention, when preparing anode, in step (1) when dissolution vfanadium compound, water is preferably
Deionized water.For the method for stirring, there is no particular limitation, can be the method for various stirrings commonly used in the art, such as can
Think electric stirring, magnetic agitation, glass bar stirring etc., under preferable case, the method for stirring is magnetic agitation.For stirring
There is no particular limitation for speed, as long as vfanadium compound can be made to dissolve, such as can be 100-300rpm.For dissolving vanadium
There is no particular limitation for temperature when compound, can be 10-40 DEG C.
In aluminum secondary battery of the invention, when preparing anode, for vfanadium compound, there is no particular limitation, can be this
The common various vfanadium compound in field.Under preferable case, vfanadium compound is vanadic anhydride, vanadium dioxide, vanadium trioxide, grass
One of sour vanadium, vanadyl oxalate and ammonium metavanadate are a variety of.
In aluminum secondary battery of the invention, when preparing anode, the present inventor is under study for action it has furthermore been found that work as
The solution that can dissolve vfanadium compound being added is aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia spirit
When equal aqueous solutions, increase the amount that can dissolve the solute in the aqueous solution of vfanadium compound, allows to dissolve the water-soluble of vfanadium compound
Solute in liquid is conducive to barium oxide in the uniform deposition of collection liquid surface relative to vfanadium compound excess.It is therefore preferable that feelings
Under condition, vfanadium compound with can dissolve solute in the aqueous solution of vfanadium compound molar ratio be 1:5-25, further preferably 1:
10-24。
In aluminum secondary battery of the invention, prepare anode when, the present inventor under study for action it has furthermore been found that with
Vanadium meter, when the concentration of the vanadium ion solution obtained in step (1) is 0.03-0.3mol/L, preferably 0.05-0.15mol/L,
Be conducive to barium oxide in the uniform deposition of collection liquid surface.Therefore, when water is added in vfanadium compound, vfanadium compound is controlled
With the amount of the water of addition, so that in terms of vanadium, the concentration of vanadium ion solution is 0.03-0.3mol/L, preferably 0.05-0.15mol/
L；When addition can dissolve aqueous solution (such as aqueous hydrogen peroxide solution, oxalic acid aqueous solution, the hydrochloric acid of vfanadium compound in vfanadium compound
Aqueous solution or ammonia spirit) when, control vfanadium compound and the molar ratio that can dissolve solute in the aqueous solution of vfanadium compound are 1:
5-25, preferably 1:10-24, and the total volume of last solution is controlled, so that the concentration of vanadium ion solution is 0.03- in terms of vanadium
0.3mol/L, preferably 0.05-0.15mol/L.
In aluminum secondary battery of the invention, when preparing anode, collector plays the effect of conducting base, for collector
There is no particular limitation, can be various collectors commonly used in the art.Under preferable case, collector be nickel foam, foam copper,
Titanium foam, foam iron-nickel, stainless (steel) wire or carbon cloth.
In aluminum secondary battery of the invention, when preparing anode, for closed container, there is no particular limitation, can be for not
With the various containers of vanadium ion solution reaction, such as can be polytetrafluoroethyllining lining stainless steel cauldron.
In aluminum secondary battery of the invention, when preparing anode, in order to be more advantageous to barium oxide in collection liquid surface
Uniform deposition, under preferable case, the mass ratio of vanadium ion solution and collector is 200:1-10:1, further preferably 100:1-
20:1.The present inventor has found under study for action, as above controls the amount of the vanadium ion solution and collector in closed container, energy
Enough make the deposition 1-30mg/cm of barium oxide on a current collector2, preferably 2-10mg/cm2。
In aluminum secondary battery of the invention, when preparing anode, in order to keep hydro-thermal reaction more abundant, it is more advantageous to vanadium oxygen
Compound is in the uniform deposition of collection liquid surface, and under preferable case, the condition of hydro-thermal reaction includes: that heating temperature is 180-205 DEG C,
Heating time is 1-4 days.
In aluminum secondary battery of the invention, when preparing anode, in order to remove the water-solubility impurity and oil in reaction product
Solubility impurity, under preferable case, the condition of cleaning includes: to be respectively washed reaction product with deionized water and organic solvent.For
It is not particularly limited, can first be cleaned with deionized water with the sequence that deionized water and organic solvent clean, it can also be first with having
Solvent cleaning.For organic solvent, there is no particular limitation, can be can to remove each of oil soluble impurity in reaction product
Kind organic solvent, such as can be dehydrated alcohol.For the number of cleaning, there is no particular limitation, produces as long as reaction can be removed
Water-solubility impurity and oil soluble impurity in object, such as can be 3-5 times.
In aluminum secondary battery of the invention, when preparing anode, under preferable case, vacuum drying condition includes: drying
Temperature is 60-80 DEG C, drying time 12-24h.
In aluminum secondary battery of the invention, when preparing anode, in order to turn the amorphous structure of barium oxide preferably
It to crystalline structure and is formed in active material barium oxide on collector strongerly, and further increases putting for battery
Electric specific capacity and cyclical stability, under preferable case, the method for preparing anode further includes that the combination for obtaining step (2) carries out
Heat treatment, it is further preferred that it is 300-600 DEG C that the condition of heat treatment, which includes: temperature, time 1-6h.Wherein, heat treatment
Mode may include calcining in air or nitrogen or argon gas.
In aluminum secondary battery of the invention, when preparing anode, before heat treatment, what the present invention was prepared is grown in collection
Barium oxide on fluid is the barium oxide (VO of undefined structureX, X 1.9-2.5), it may be possible to vanadic anhydride, dioxy
Change one of vanadium, vanadium trioxide and vanadium oxide or a variety of mixtures；After heat treatment, barium oxide is by amorphous structure
Crystalline structure is turned to, the barium oxide particle of high-crystallinity is obtained.
In aluminum secondary battery of the invention, cathode can be the various negative electrode materials that can be used in assembling aluminum secondary battery,
It such as can be metallic aluminium or aluminium alloy.For the form of metal aluminum or aluminum alloy, there is no particular limitation, can be common
Various forms, in order to make battery be easier to process, under preferable case, the form of metal aluminum or aluminum alloy be powder, silk, net, piece or
Foam.
In aluminum secondary battery of the invention, for diaphragm, there is no particular limitation, can be for for assembling aluminum secondary battery
Various diaphragms, in order to improve the wellability of ionic liquid, under preferable case, diaphragm is fibreglass diaphragm.
In aluminum secondary battery of the invention, under preferable case, electrolyte is the ionic liquid of aluminium containing salt, including by aluminum halide
Halogen aluminic acid ionic liquid is formed by with any one in quaternary ammonium salt, quaternary alkylphosphonium salt, season sulfosalt, imidazolium halide salt and pyridinium halide salt
Body, or including by BF containing anion4 -、PF6 -、CF3SO3 -Or TFSI-Imidazoles, pyridine, in piperidines and pyrrolidinium ion liquid
There is the aluminium salt of identical anion to be formed by il electrolyte for any one dissolution.It is further preferred that electrolyte is
The chlorine Ion-selective electrod that aluminium chloride and imidazolium halide salt are formed, wherein the molar ratio of aluminium chloride and imidazolium halide salt is 1-
1.5:1 more preferably 1.1:1；Still further preferably, electrolyte AlCl3/[BMIM]Cl、AlCl3/[EMIM]Cl、
AlCl3/ [BMIM] Br and AlCl3Any one in/[EMIM] Br.Present inventor has found under study for action, is preparing aluminium
When secondary cell, when the imidazolium halide salt in electrolyte is appointing in [BMIM] Cl, [EMIM] Cl, [BMIM] Br and [EMIM] Br
When anticipating a kind of, imidazolium halide salt such as chlorination 1- amyl -3- methylimidazole ([PMIM] Cl), the trialkyl replaced with long-chain replaces
Imidazolium halide salt such as chlorination 1- butyl -2,3- methylimidazole ([BDiMIM] Cl) is compared, and the viscous of electrolyte can be substantially reduced
Degree, raising conductivity significantly improve the electrochemistry of aluminum secondary battery to significantly improve the wellability of electrolyte and electrode material
Performance.
In aluminum secondary battery of the invention, for the shape of the aluminum secondary battery being assembled into, there is no particular limitation, can be with
For those skilled in the art it is conceivable that various shape, such as aluminum secondary battery can be button cell or cylindrical battery.
In the present invention, for the preparation method of aluminum secondary battery, there is no particular limitation, can be commonly used in the art each
Kind preparation method, for example, using the combination of the barium oxide and collector that grow on a current collector as anode, metallic aluminium conduct
Cathode, acid chlorization aluminium profiles ionic liquid can be assembled into argon gas glove box as electrolyte using fibreglass diaphragm
Aluminum secondary battery.For the specific method of assembling, there is no particular limitation, can be various methods commonly used in the art, herein not
It repeats again.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In following embodiment, being scanned the scanning electron microscope used when Electronic Speculum observation is field emission scanning electron microscope (Hitachi
Hitachi S-4800)。
Using the structural form of Rigaku DMAX2400 type X-ray diffractometer characterization barium oxide.
Using inductive coupling plasma emission spectrograph (Profile, Leeman company, the U.S.) analysis barium oxide
Element composition.
Vanadium pentoxide powder, oxalic acid, vanadyl oxalate powder and ammonium metavanadate powder are purchased from Chinese medicines group chemical reagent
Beijing Co., Ltd.
Fibreglass diaphragm is Whatman glass fiber filter paper GF/C (1822-047).
The measuring method of the deposition of barium oxide on a current collector are as follows: weigh the quality of collector before hydro-thermal reaction respectively
With vacuum drying/calcined collector for being deposited with barium oxide quality, the quality difference value of the two and collector it is apparent
(by taking embodiment 1 as an example, the apparent area of every nickel foam is 3 × 4cm to area2) ratio be barium oxide on a current collector
Deposition.
Embodiment 1
The present embodiment is for illustrating aluminum secondary battery of the invention.
30ml deionized water is added at 25 DEG C in 0.364g vanadium pentoxide powder and passes through magnetic agitation (150rpm)
It is mixed, aqueous hydrogen peroxide solution (vanadic anhydride and the hydrogen peroxide of 5ml30 weight % is added while magnetic agitation
Molar ratio be 1:22), continuation stirs 0.5h at 150rpm, and obtaining concentration is that the transparent of 0.11mol/L orange red crosses vanadium
Acid solution (concentration is in terms of vanadium).Then obtained pervanadic acid solution all (36.1g) is transferred to 50ml polytetrafluoroethyllining lining
Stainless steel cauldron in, be added four 3 × 4cm2Nickel foam (aperture 110PPI, thickness 1mm, every quality is 0.4g),
Heating reaction 3 days, are cooled to 25 DEG C after completion of the reaction at 190 DEG C, take out reaction product and are first washed 2 times with dehydrated alcohol, then
It is washed with deionized 2 times, it is then 20 hours dry at 70 DEG C in a vacuum drying oven, finally forged at 500 DEG C in air
4h is burnt, the combination for obtaining being grown in barium oxide and nickel foam in nickel foam after the disk that diameter is 1cm is cut into.
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
The XRD spectrum of barium oxide prepared by embodiment 1 is as shown in Figure 1.Through inductive coupling plasma emission spectrograph
(ICP) it tests, and combines Fig. 1 it is found that obtained barium oxide is the barium oxide (VO of undefined structure before heat treatmentX, X
For 2.48), it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixtures；?
After being heat-treated in air, the good V of crystallinity has been obtained2O5Particle.
The barium oxide being prepared before embodiment 1 is heat-treated is observed under scanning electron microscope, scanning electron microscope (SEM) photograph
(SEM figure) is shown in Fig. 2.From figure 2 it can be seen that the barium oxide that embodiment 1 is prepared before being heat-treated is in Nanoparticulate shape
Looks are grown in nickel foam substrate surface, partial size about 400nm.Fig. 3 is the barium oxide being prepared after embodiment 1 is heat-treated
SEM figure, from figure 3, it can be seen that the pattern of the barium oxide after heat treatment is preceding almost the same with heat treatment.
It is secondary as aluminium using the combination of the barium oxide being grown in nickel foam being prepared of embodiment 1 and nickel foam
Anode, using metal aluminium flake as cathode, with acid chlorization aluminium profiles imidazolium ionic liquid AlCl3/ [BMIM] Cl=1.1:1
(molar ratio) is assembled into aluminium secondary button cell (2025 types using fibreglass diaphragm for electrolyte in argon gas glove box
Number).
Embodiment 2
The present embodiment is for illustrating aluminum secondary battery of the invention.
At 25 DEG C, 0.364g vanadium pentoxide powder is weighed according to the ratio that molar ratio is 1:10 and 1.8g oxalic acid directly adds
Enter into 72ml deionized water, 3h is persistently stirred by magnetic agitation (200rpm) to transparent dark blue solution is formed, is obtained
Concentration is the vanadyl oxalate solution of 0.056mol/L (concentration is in terms of vanadium).Then obtained solution all (74.1g) is transferred to
In the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, 3 × 4cm of two panels is added2Foam iron-nickel (aperture 110PPI, thickness
1mm, every quality are 0.4g), it is reacted 4 days in 180 DEG C of heating.It is cooled to 25 DEG C after completion of the reaction, it is first to take out reaction product
It is washed 2 times with dehydrated alcohol, then is washed with deionized 2 times, it is then 24 hours dry at 60 DEG C in a vacuum drying oven, finally
6h is calcined at 300 DEG C in argon gas, is cut into diameter to obtain being grown in the barium oxide on foam iron-nickel after the disk of 1cm
With the combination of foam iron-nickel.
After measured, deposition of the barium oxide on foam iron-nickel is 6mg/cm2。
The barium oxide that embodiment 2 is prepared is through X-ray diffraction and inductive coupling plasma emission spectrograph (ICP)
Test, learns, obtained barium oxide is the barium oxide (VO of undefined structure before heat treatmentX, X 1.9), it may be possible to five
One of V 2 O, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixtures；After being heat-treated in argon gas,
The good barium oxide particle (VO of crystallinity is obtainedX, X 1.9).
The barium oxide that embodiment 2 is prepared is observed under scanning electron microscope, wherein be prepared after heat treatment
The SEM figure of barium oxide see Fig. 4, from fig. 4, it can be seen that the barium oxide particle that embodiment 2 is prepared after being heat-treated is in
It is flower-shaped to be grown in foam iron-nickel matrix surface, partial size about 3um.It should be noted simultaneously that the vanadium before embodiment 2 is heat-treated aoxidizes
Almost the same after the pattern of object and heat treatment, details are not described herein.
The combination of the barium oxide being grown on foam iron-nickel and foam iron-nickel that are prepared using embodiment 2 is as aluminium
Anode of secondary battery, using Filamentous aluminium alloy as cathode, with chlorine Ion-selective electrod AlCl3/ [BMIM] Br=1.1:1 (mole
Than) it is that electrolyte using fibreglass diaphragm is assembled into the secondary button cell of aluminium (2025 model) in argon gas glove box.
Embodiment 3
The present embodiment is for illustrating aluminum secondary battery of the invention.
At 25 DEG C, 0.702g ammonium metavanadate is weighed according to the ratio that molar ratio is 1:5 and 2.7g oxalic acid is added directly into
In 40ml deionized water.1h is persistently stirred by magnetic agitation (150rpm) until forming clear solution, obtaining concentration is
(the NH of 0.15mol/L4)2[(VO)2(C2O4)3] solution (concentration is in terms of vanadium).Then by all (43.4g) transfers of obtained solution
Into the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, four 3 × 4cm are added2Foam copper (aperture 110PPI, thickness
1mm, every quality are 0.4g), and heating reaction 1 day, is cooled to 25 DEG C after completion of the reaction at 205 DEG C, and it is first to take out reaction product
It is washed with deionized 2 times, then washs 2 times with dehydrated alcohol, it is then 12 hours dry at 80 DEG C in a vacuum drying oven, finally
Calcine 1h at 600 DEG C in nitrogen, be cut into after the disk that diameter is 1cm obtain being grown in barium oxide on foam copper with
The combination of foam copper.
After measured, deposition of the barium oxide on foam copper is 10mg/cm2。
The barium oxide that embodiment 3 is prepared is through X-ray diffraction and inductive coupling plasma emission spectrograph (ICP)
Test, learns, obtained barium oxide is the barium oxide (VO of undefined structure before heat treatmentX, X 2.17), it may be possible to
One of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixtures；It is heat-treated in nitrogen
Afterwards, the good barium oxide particle (VO of crystallinity has been obtainedX, X 2.17).
The barium oxide that embodiment 3 is prepared is observed under scanning electron microscope, wherein be prepared after heat treatment
The SEM figure of barium oxide see Fig. 5, from fig. 5, it can be seen that the barium oxide particle that embodiment 3 is prepared after being heat-treated is in
Palpus shape is grown in foam copper matrix surface.It should be noted simultaneously that the pattern and heat of the barium oxide before the heat treatment of embodiment 3
Almost the same after processing, details are not described herein.
The combination of the barium oxide being grown on foam copper and foam copper that are prepared using embodiment 3 is secondary as aluminium
Anode, using net metal aluminium as cathode, with chlorine Ion-selective electrod AlCl3/ [EMIM] Cl=1.5:1 (molar ratio) is
Electrolyte is assembled into aluminium secondary circle cylindrical cell (18650 model) using fibreglass diaphragm in argon gas glove box.
Embodiment 4
The present embodiment is for illustrating aluminum secondary battery of the invention.
At 25 DEG C, 40ml deionized water is added in 0.49g vanadyl oxalate powder and is held by magnetic agitation (150rpm)
Continuous stirring 2h, obtains the blue vanadium ion solution that concentration is 0.05mol/L (concentration is in terms of vanadium).Then by solution whole
(40.49g) is transferred in the stainless steel cauldron of 50ml polytetrafluoroethyllining lining, and four 3 × 4cm are added2Stainless (steel) wire (1000
Mesh, every quality are 0.5g), it is reacted 1 day in 180 DEG C of heating, is cooled to 25 DEG C after completion of the reaction, taken out reaction product and first use
Dehydrated alcohol washs 2 times, then is washed with deionized 2 times, then 12 hours dry at 80 DEG C in a vacuum drying oven, finally exists
Calcine 6h at 300 DEG C in air, be cut into after the disk that diameter is 1cm obtain being grown in barium oxide on stainless (steel) wire with
The combination of stainless (steel) wire.
After measured, deposition of the barium oxide on stainless (steel) wire is 0.5mg/cm2。
The barium oxide that embodiment 4 is prepared is through X-ray diffraction and inductive coupling plasma emission spectrograph (ICP)
Test, learns, obtained barium oxide is the barium oxide (VO of undefined structure before heat treatmentX, X 1.95), it may be possible to
One of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixtures；It is heat-treated in air
Afterwards, barium oxide has obtained the good V of crystallinity through oxidation2O5Particle.
The barium oxide that embodiment 4 is prepared is observed under scanning electron microscope, wherein be prepared after heat treatment
The SEM figure of barium oxide see Fig. 6, from fig. 6, it can be seen that the barium oxide particle that embodiment 4 is prepared after being heat-treated is in
Lamellar growth is in stainless (steel) wire matrix surface.It should be noted simultaneously that embodiment 4 be heat-treated before barium oxide pattern with
Almost the same after heat treatment, details are not described herein.
The combination of the barium oxide being grown on stainless (steel) wire and stainless (steel) wire that are prepared using embodiment 4 is as aluminium
Anode of secondary battery, using foamed metal aluminium as cathode, with chlorine Ion-selective electrod AlCl3/ [EMIM] Br=1:1 (mole
Than) it is that electrolyte using fibreglass diaphragm is assembled into aluminium secondary circle cylindrical cell (18650 model) in argon gas glove box.
Embodiment 5
Anode and battery is prepared according to the method for embodiment 1, unlike, it is water-soluble that 1ml30 weight % hydrogen peroxide is added
Liquid (molar ratio of vanadic anhydride and hydrogen peroxide is 1:4.4).
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 6
Anode and battery is prepared according to the method for embodiment 1, unlike, 100ml is added in vanadium pentoxide powder
Deionized water obtains the transparent orange red pervanadic acid solution that concentration is 0.038mol/L (concentration is in terms of vanadium).
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 7
Anode and battery is prepared according to the method for embodiment 1, unlike, after aqueous hydrogen peroxide solution is added, continue to stir
Mix 4h.
After measured, deposition of the barium oxide in nickel foam is 1mg/cm2。
Embodiment 8
Anode and battery is prepared according to the method for embodiment 1, unlike, it is 1cm that 4 areas, which are added,2Nickel foam disk
(aperture 110PPI, thickness 1mm, every quality is 0.03g).
After measured, deposition of the barium oxide in nickel foam is 20mg/cm2。
Embodiment 9
Anode and battery is prepared according to the method for embodiment 1, unlike, it is added after nickel foam and is heated instead at 190 DEG C
Answer 12h.
After measured, deposition of the barium oxide in nickel foam is 0.5mg/cm2。
Embodiment 10
Anode and battery is prepared according to the method for embodiment 1, unlike, after 70 DEG C are 20 hours dry, without forging
It burns, is directly cut into the disk that diameter is 1cm.
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
Embodiment 11
Anode and battery is prepared according to the method for embodiment 1, unlike, after 70 DEG C are 20 hours dry, in air
4h is calcined at 150 DEG C.
After measured, deposition of the barium oxide in nickel foam is 2mg/cm2。
The XRD spectrum for the barium oxide that embodiment 5-9 and embodiment 11 are prepared is similar to Example 1, embodiment
The XRD spectrum of 10 barium oxides being prepared is referring to the map before calcining in Fig. 1.And emit light through inductively coupled plasma body
Spectrometer (ICP) test, learns, is unformed knot before the barium oxide heat treatment that embodiment 5-9 and embodiment 11 are prepared
The barium oxide of structure, it may be possible to one of vanadic anhydride, vanadium dioxide, vanadium trioxide and vanadium oxide or a variety of mixing
Object；After heat treatment, the good barium oxide of crystallinity has been obtained.The barium oxide that embodiment 10 is prepared still is without fixed
The barium oxide of type structure.
The barium oxide being prepared before embodiment 5-11 heat treatment and after heat treatment is observed under scanning electron microscope,
SEM figure is similar to Example 1 respectively, that is, barium oxide that embodiment 5-11 is prepared (including through Overheating Treatment and without
The barium oxide of Overheating Treatment) collection liquid surface is grown in Nanoparticulate pattern.
Embodiment 12
Anode and battery is prepared according to the method for embodiment 1, unlike, with AlCl3/ [PMIM] Cl=1.1:1 (mole
Than) it is electrolyte.
Embodiment 13
Anode and battery is prepared according to the method for embodiment 1, unlike, with AlCl3/ [BDiMIM] Cl=1.1:1 (rubs
That ratio) it is electrolyte.
Test example
Respectively to embodiment 1-13 group on LAND CT2001A tester (being purchased from Wuhan Land Electronic Co., Ltd.)
It fills obtained aluminum secondary battery and carries out constant current charge-discharge performance test, charging/discharging voltage range is 2.5-0.02V, charging and discharging currents
Density is 44.2mA/g.Wherein, the first discharge specific capacity for the battery that embodiment 1-13 is assembled into is (with the quality of positive electrode
Meter) and recycle 50 times after specific discharge capacity (in terms of the quality of positive electrode) be shown in Table 1.
Table 1
In aluminum secondary battery of the invention, barium oxide, which is grown directly upon on collector, forms anode, does not need addition and leads
Electric agent and binder, that is, may make not only has electrical contact well between the two, is able to maintain the steady of good anode electrode
It is qualitative, and it is capable of increasing the surface area of vanadium oxide positive electrode materials, the contact area of positive electrode and electrolyte is improved, is shortened
Diffusion length needed for aluminium ion and electronics, meanwhile, aluminum secondary battery of the invention specific discharge capacity with higher and excellent
Stable circulation performance.
Embodiment 1 and embodiment 5 are compared it is found that when preparing anode vfanadium compound and vfanadium compound can be dissolved
When the molar ratio of solute is 1:10-24 in aqueous solution, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can
Further increase the specific discharge capacity and stable circulation performance of battery.
Embodiment 1 and embodiment 6 are compared it is found that in terms of vanadium, the concentration of vanadium ion solution is when preparing anode
When 0.05-0.15mol/L, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can further increase battery
Specific discharge capacity and stable circulation performance.
Embodiment 1 and embodiment 7 are compared it is found that when preparing anode, with hydrogen peroxide aqueous dissolution vfanadium compound,
And when the time of stirring is 0.5-3h, barium oxide is more advantageous in the uniform deposition of collection liquid surface, and can be further
Improve the specific discharge capacity and stable circulation performance of battery.
Embodiment 1 and embodiment 8 are compared it is found that the mass ratio of vanadium ion solution and collector is when preparing anode
When 100:1-20:1, the specific discharge capacity and stable circulation performance of battery can be further increased.
Embodiment 1 and embodiment 9 are compared it is found that prepare anode when, extend in closed container hydro-thermal reaction when
Between, when heated between when being 1-4 days so that react more abundant, be more advantageous to barium oxide in the uniform deposition of collection liquid surface,
And the specific discharge capacity and stable circulation performance of battery can be further increased.
Embodiment 1 and embodiment 10-11 are compared it is found that when preparing anode, the combination that will be obtained after vacuum drying
It is heat-treated and the temperature being heat-treated is 300-600 DEG C, when the time is 1-6h, although not will increase barium oxide in collector
On deposition be still but conducive to the raising of the crystallinity of barium oxide, the specific discharge capacity of battery can be further increased
And stable circulation performance.
Embodiment 1-11 (especially embodiment 1) and embodiment 12-13 are compared it is found that when preparing aluminum secondary battery,
When electrolyte is AlCl3/[BMIM]Cl、AlCl3/[EMIM]Cl、AlCl3/ [BMIM] Br and AlCl3It is any in/[EMIM] Br
When a kind of, the specific discharge capacity and stable circulation performance of battery can be further increased.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. a kind of aluminum secondary battery, which is characterized in that the aluminum secondary battery includes anode, cathode, electrolyte and diaphragm, described
Electrolyte is AlCl3/[BMIM]Cl、AlCl3/[EMIM]Cl、AlCl3/ [BMIM] Br and AlCl3It is any one in/[EMIM] Br
Kind, the anode is the combination for growing barium oxide and collector on a current collector, and the preparation method of the anode includes
Following steps:
(1) vfanadium compound is dissolved, obtains the vanadium ion solution that concentration is 0.05-0.15mol/L；
(2) vanadium ion solution and collector are subjected in closed container hydro-thermal reaction, clean reaction product after reaction
And vacuum drying, obtain growing the combination of barium oxide and collector on a current collector；
(3) combination that step (2) obtains is calcined, the condition of the calcining includes: that temperature is 300-600 DEG C, the time
For 1-6h；
Wherein, in step (2), the mass ratio of the vanadium ion solution and the collector is 100:1-20:1, and the water
The condition of thermal response includes: that heating temperature is 180 DEG C to less than 205 DEG C, and heating time is 1-4 days, and the barium oxide is in institute
Stating the deposition on collector is 2-10mg/cm2。
2. aluminum secondary battery according to claim 1, wherein in step (2), the vacuum drying condition includes: dry
Dry temperature is 60-80 DEG C, drying time 12-24h.
3. aluminum secondary battery according to claim 1 or 2, wherein in step (1), the method for dissolving vfanadium compound includes:
Under stiring, the solution that can dissolve vfanadium compound is added in vfanadium compound；The solution that vfanadium compound can be dissolved is
Water, aqueous hydrogen peroxide solution, oxalic acid aqueous solution, aqueous hydrochloric acid solution or ammonia spirit.
4. aluminum secondary battery according to claim 1 or 2, wherein the vfanadium compound is vanadic anhydride, titanium dioxide
One of vanadium, vanadium trioxide, vanadium oxalate, vanadyl oxalate and ammonium metavanadate are a variety of.
5. aluminum secondary battery according to claim 1 or 2, wherein the collector be nickel foam, foam copper, titanium foam,
Foam iron-nickel, stainless (steel) wire or carbon cloth.
6. aluminum secondary battery according to claim 1 or 2, wherein the cathode is metal aluminum or aluminum alloy；The diaphragm
For fibreglass diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410336027.8A CN105261784B (en) | 2014-07-15 | 2014-07-15 | A kind of aluminum secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410336027.8A CN105261784B (en) | 2014-07-15 | 2014-07-15 | A kind of aluminum secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105261784A CN105261784A (en) | 2016-01-20 |
| CN105261784B true CN105261784B (en) | 2019-05-10 |
Family
ID=55101358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410336027.8A Expired - Fee Related CN105261784B (en) | 2014-07-15 | 2014-07-15 | A kind of aluminum secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105261784B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810898A (en) * | 2016-03-10 | 2016-07-27 | 中国科学院金属研究所 | Preparation method of amorphous carbon/carbon composite electrode material for aluminum secondary battery |
| TWI685489B (en) * | 2017-01-25 | 2020-02-21 | 財團法人工業技術研究院 | Aluminum-ion battery |
| CN106941188B (en) * | 2017-05-03 | 2019-01-29 | 厦门大学 | One kind can charge and discharge aluminium ion battery and its preparation process |
| CN108376795B (en) * | 2018-04-04 | 2020-08-18 | 天津大学 | Dendrite-free high-rate aluminum ion battery |
| CN108493502B (en) * | 2018-04-13 | 2021-05-11 | 深圳市得朗高科技有限公司 | Double-carbon and double-MXene pole ion high-performance battery |
| JP6792741B2 (en) * | 2018-10-10 | 2020-11-25 | 住友化学株式会社 | Non-aqueous electrolyte Negative electrode for secondary batteries Active material, negative electrode, battery and aluminum clad metal laminate |
| CN109888395A (en) * | 2019-01-14 | 2019-06-14 | 浙江大学 | Aluminium ion cell electrolyte solution and battery |
| CN110571060B (en) * | 2019-06-24 | 2021-06-11 | 北京科技大学 | Preparation method of vanadium dioxide/foamed nickel integrated electrode |
| CN111682265A (en) * | 2020-06-04 | 2020-09-18 | 北京理工大学 | Aluminum secondary battery |
| CN113358558B (en) * | 2021-05-31 | 2023-02-03 | 燕山大学 | Method for bonding nano material in-situ electron microscope |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767771B (en) * | 2010-01-08 | 2013-03-20 | 武汉理工大学 | Preparation method of vanadium oxide/carbon nanometer tube composite materials with interpenetrating network structures |
-
2014
- 2014-07-15 CN CN201410336027.8A patent/CN105261784B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105261784A (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105261784B (en) | A kind of aluminum secondary battery | |
| CN105304885B (en) | A kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof | |
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| CN104617288B (en) | A kind of copper-based rich sodium layered oxide material and its production and use | |
| CN104617271B (en) | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof | |
| CN111697210A (en) | Sodium ion battery multi-element positive electrode material and preparation method thereof | |
| CN109980272A (en) | A kind of Al doping sheet LLZO composite solid electrolyte and its preparation method and application | |
| CN103259009B (en) | A kind of water-system alkali metal ion electrochemical energy storing device | |
| CN108545774A (en) | Porous vanadic anhydride micron ball electrode material and its preparation method and application | |
| CN108987711A (en) | A kind of spherical shape sodium-ion battery anode quaternary material and preparation method thereof | |
| CN106328918B (en) | A kind of NiTiO for sodium-ion battery3/ C composite, preparation and application | |
| CN106252628A (en) | The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery | |
| CN111785942A (en) | Water-based zinc ion battery positive electrode material and preparation method and application thereof | |
| He et al. | Ultrathin (NH4) 0.5 V2O5 nanosheets as a stable anode for aqueous lithium ion battery | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN107500355A (en) | A kind of preparation method for being layered lepidocrocite type nanometer strip vanadium dioxide | |
| CN115057485A (en) | Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof | |
| CN108831755A (en) | A kind of preparation method of electrode for capacitors multi-element composite material | |
| CN107275615A (en) | A kind of sulphur copper compound C-base composte material is the aluminium ion battery of positive pole | |
| CN108933243A (en) | A kind of height ratio capacity sodium-ion battery positive material and preparation method thereof and sodium-ion battery | |
| CN108963242A (en) | A kind of unformed sodium-ion battery positive material and preparation method thereof and sodium-ion battery | |
| Liu et al. | A quick microwave-assisted rheological phase reaction route for preparing Cu3Mo2O9 with excellent lithium storage and supercapacitor performance | |
| CN104241628A (en) | Method for preparing titanium-dioxide-modified ferric oxide microspheres as well as produced product and use of titanium-dioxide-modified ferric oxide microspheres | |
| CN110071282A (en) | A kind of bismuth phosphate composite reduction graphene oxide composite material and its preparation method and application | |
| CN110336015A (en) | A kind of preparation method of carbon coating tin and tin ferroalloy lithium ion battery negative material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190510 |