CN107240714A - One kind can discharge and recharge aluminium ion battery and preparation method thereof - Google Patents
One kind can discharge and recharge aluminium ion battery and preparation method thereof Download PDFInfo
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- CN107240714A CN107240714A CN201710514489.8A CN201710514489A CN107240714A CN 107240714 A CN107240714 A CN 107240714A CN 201710514489 A CN201710514489 A CN 201710514489A CN 107240714 A CN107240714 A CN 107240714A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
One kind can discharge and recharge aluminium ion battery and preparation method thereof, be related to aluminium ion battery.Including anode, GND, electrolyte, collector, barrier film；Anode is Prussian blue and its derivative, and GND is metallic aluminium or aluminium-containing alloy.Described Prussian blue and its derivative chemical general formula is：AxM[N(CN)6]y·nH2O.Prussian blue and its derivative, conductive material, binding agent are mixed；Aluminum or aluminum alloy is polished two-sided, cell negative electrode material is obtained；After ionic liquid is dried, aluminum halide and ionic liquid mixing are obtained containing can move freely aluminum ions nonaqueous solution electrolysis liquid；It will estimate after positive electrode, negative material, electrolyte, barrier film assembling, obtain the aluminium ion battery that Prussian blue and its derivative is positive pole.
Description
Technical field
, can discharge and recharge aluminium ion battery and preparation method thereof more particularly, to one kind the present invention relates to aluminium ion battery.
Background technology
Lithium ion battery is considered as one of most promising electrochemical energy storage system always because its energy density it is high,
Have extended cycle life, work potential it is high.But recently as a wide range of promotion and application of lithium ion battery, lithium resource faces withered
Exhaust, price rises year by year.And bauxite resource is abundant, annual yield is more than 1000 times of lithium, cheap；Secondly, aluminum honeycomb exists
Property is stable in air, and safety coefficient is high；Furthermore, its energy density per unit volume metric density is significantly larger than lithium, and additional aluminium ion battery also has
Bendable folding endurance is strong, it is environmentally friendly the advantages of, therefore for following wearable device battery, easily collide it is dangerous it is inflammable easily
There is great application prospect in quick-fried automobile batteries, the field such as extensive intelligent grid energy storage.
At present, the research of aluminium ion battery is still in initial stage, and positive electrode can select narrow range, in the aluminium having been reported that
In ion battery positive electrode, such as Mo of Cheverel phase structures6S8Positive active material can be good at reversible embedding de- Al (texts
Offer:Geng,L.X.et al.Reversible electrochemical intercalation of aluminum in
Mo6S8.Chemistry of Materials [J], 2015), its first circle specific discharge capacity is 148mA h g-1, but the material system
Standby condition is harsh, and cost is high, therefore practicality is little.And for example embedding off line manages section bar strand foam graphite (document:Lin,M.C.et
Al.An ultrafast rechargeable aluminium-ion battery [J] .Nature, 2015), research is using heat
Graphite and three-dimensional foam graphite are solved as aluminium ion cell positive material, cycle performance is although excellent, but its preparation technology is especially
Complexity, commercialization is almost difficult to.
Prussian blue and its derivative has excellent electrochemical reversibility, and the stability of height is easily prepared and valency
The advantages of lattice are cheap, thus have very big application prospect in terms of electrochemical catalysis, electricity colour developing, secondary cell.In addition, general Shandong
Scholar is blue and its derivative has zeolite characteristic, can be quickly occur exchange reaction with alkali metal ion.There is substantial amounts of sky therebetween
Gap, is easy to the insertion and deintercalation of ion, and transition metal therein has different valence state, can occur redox reaction,
Electro transfer is provided.According to these features, Prussian blue and its derivative has larger in terms of as lithium ion battery material
Advantage.Lian Shen et al. have studied Prussian blue and its derivative Berlin green as anode material for lithium-ion batteries
Charge-discharge performance (document:Lian,S.et al.Prussian Blues as a Cathode Material for Lithium
Ion Batteries [J] .Chemistry A European Journal, 2014), Fe [Fe (CN)6] first circle discharge capacity
Reach 138mAh/g, capacity attenuation is to 96mAh/g after the circle of circulation 50, and Fe4[Fe(CN)6]3First circle discharge capacity reach
After 95mAh/g, the circle of circulation 50, capacity attenuation 25%.The coulombic efficiency of two kinds of materials has reached 99% in some number of turns, this display
The material structure high stability in the range of the voltage range.Its high charge-discharge specific capacity of prussian blue and its excellent follow
Ring performance provides transmission mainly due to a large amount of gap structures present in its space structure, these gap structures for lithium ion
Passage and storage area.Above result of study all shows prussian blue material in economical and easily available, environment-friendly secondary cell
There is important application value in field.
The patent as aluminium ion cell positive material on Prussian blue and its derivative is not yet reported so far.
The content of the invention
Can discharge and recharge aluminium ion battery and preparation method thereof it is an object of the invention to provide one kind.
It is described can discharge and recharge aluminium ion battery include anode, GND, electrolyte, collector, barrier film；The electricity
Solution liquid is non-aqueous electrolyte containing aluminium ion, and the collector is the tinsel afflux for showing electrochemicaUy inert in the electrolytic solution
Body, the barrier film is the barrier film for separating anode and GND, wherein, anode is Prussian blue and its derivative,
GND is metallic aluminium or aluminium-containing alloy；
Described Prussian blue and its derivative chemical general formula is：AxM[N(CN)6]y·nH2O, wherein A are alkali metal, choosing
One kind from K or Na；M, N are transition metal, selected from one or both of Fe, Cu, Ni, Co, Mn, Cr etc..
Described Prussian blue and its derivative preparation method is as follows：
1) Prussian blue preparation method：It is Prussian blue to be obtained by simple liquid phase method, weigh 0.01mol six water
Close iron chloride (FeCl3·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Equally weigh
0.005mol three six POTASSIUM FERROCYANIDE 99 (K of hydration4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to
0.1mol/L K4[Fe(CN)6] solution.By FeCl3Solution is added dropwise in K by distribution type peristaltic pump with 1mL/min speed4
[Fe(CN)6] in solution, electric stirring 6h under 60 DEG C of water bath conditions, mixing speed is 250r/min, then naturally cools to room
Temperature, centrifugation, is cleaned for several times with deionized water and acetone, obtained sample is placed on into vacuum drying chamber and is dried overnight, temperature is set
60 DEG C are set to, next day, grinding obtains Prussian blue dark blue powder (Fe4[Fe(CN)6]3)。
2) preparation method of Prussian blue analog derivative：
(1) preparation of Berlin green：Berlin green can also be prepared by liquid phase method, weigh 0.01mol ferric chloride hexahydrate
(FeCl3·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Equally weigh 0.005mol's
Hexacyanoferrate potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.
By FeCl3Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed3[Fe(CN)6] in solution, in 40 DEG C of water
Electric stirring 6h under the conditions of bath, mixing speed is 250r/min, then stands reaction solution to room temperature, centrifugation, uses deionized water
With acetone cleaning for several times, obtained sample is placed on vacuum drying chamber and is dried overnight, temperature setting is 60 DEG C, next day, grinding,
Obtain the blackish green powder of Berlin green (Fe [Fe (CN)6])。
(2) grass green powder (Nix[Fey(CN)6]) preparation：Weigh 0.01mol Nickel dichloride hexahydrate (NiCl2·
6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Equally weigh 0.005mol three hydrations six
POTASSIUM FERROCYANIDE 99 (K4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K4[Fe(CN)6] molten
Liquid.By NiCl2Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed4[Fe(CN)6] in solution, room temperature
Under the conditions of electric stirring 6h, mixing speed is 250r/min, centrifugation, cleaned with deionized water and acetone for several times, by obtained sample
Product are placed on vacuum drying chamber and are dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains grass green powder (Nix[Fey
(CN)6])。
(3) brownish-yellow powder (Nix[Fey(CN)6]) preparation：Weigh 0.01mol Nickel dichloride hexahydrate (NiCl2·
6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Six cyanogen for equally weighing 0.005mol close iron
Sour potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By NiCl2It is molten
Liquid is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed3[Fe(CN)6] in solution, electric mixing under room temperature condition
6h is mixed, mixing speed is 250r/min, centrifuge, cleaned with deionized water and acetone for several times, obtained sample is placed on vacuum
Drying box is dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains brownish-yellow powder (Nix[Fey(CN)6])。
(4) celadon powder (Cux[Fey(CN)6]) preparation：Weigh 0.01mol Copper dichloride dihydrate (CuCl2·
2H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L CuCl2Solution；Six cyanogen for equally weighing 0.005mol close iron
Sour potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By K3[Fe
(CN)6] solution is slowly added dropwise in CuCl by distribution type peristaltic pump with 1mL/min speed2It is electronic under room temperature condition in solution
6h is stirred, mixing speed is 250r/min, centrifugation is cleaned for several times with deionized water and acetone, obtained sample is placed on very
Empty drying box is dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains celadon powder (Cux[Fey(CN)6])。
(5) celadon powder (Cux[Fey(CN)6]) preparation：Weigh 0.015mol copper acetate (Cu (OOCCH3)2), it is molten
In 150mL deionized waters, 0.1mol/L Cu (OOCCH are configured to3)2Solution；Equally weigh 0.01mol Hexacyanoferrate
Potassium (K3[Fe(CN)6]), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By K3[Fe
(CN)6] solution is slowly added dropwise in Cu (OOCCH by distribution type peristaltic pump with 1mL/min speed3)2In solution, room temperature condition
Lower electric stirring 6h, mixing speed is 250r/min, centrifugation, is cleaned with deionized water and acetone for several times, obtained sample is put
Put and be dried overnight in vacuum drying chamber, temperature setting is 60 DEG C, next day, grinding obtains celadon powder (Cux[Fey(CN)6])。
The cell negative electrode material is the metallic aluminium or metallic aluminium and copper, silver, nickel, lead, tin, bismuth, iron that purity is more than 90%
Deng the alloy of formation.
The non-aqueous electrolyte containing aluminium ion includes aluminum halide and ionic liquid, and the aluminum halide and ionic liquid rub
You are than being (1.1~2) ︰ 1.
The anion of the ionic liquid includes Cl-, Br-, I-, PF6 -, BF6 -, CN-, SCN-, [N (CF3SO2)2]-Or [N
(CN)2]-Plasma；Cation include imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholine from
Son, quaternary ammonium salt ion, quaternary phosphonium salt ion or tertiary sulfosalt ion etc..
The tinsel collector of the electrochemicaUy inert includes tantalum piece, niobium sheet, molybdenum sheet, titanium sheet, stainless steel substrates, gold and platinum
Race's metal.
The diaphragm material of the separation anode and GND includes but is not limited to：TPO such as polyethylene and poly-
Propylene, glass fiber filter paper and ceramic material.
It is described can the preparation method of discharge and recharge aluminium ion battery comprise the following steps：
1) Prussian blue and its derivative, conductive material, binding agent are proportionally weighed into mixing respectively, active material is made
Slurry material is applied on inert metal collector, is dried in 60~100 DEG C, and thickness is made for 0.5~2mm sheet anode composites
Material；
2) by the metal aluminum or aluminum alloy that thickness is 0.1~1mm, polish two-sided, after washes of absolute alcohol, dry, i.e.,
Obtain cell negative electrode material；
3) ionic liquid is dried into 12h at 80~150 DEG C of vacuum drying chamber, subsequent aluminum halide and ionic liquid with mole
Than for (1.1~2) ︰ 1 are mixed in the glove box of ar gas environment, magnetic agitation 0.5h, that is, are configured to containing can move freely aluminium
The nonaqueous solution electrolysis liquid of ion；
4) by step 1) obtained cell positive material, step 2) obtain cell negative electrode material, step 3) containing of obtaining
Aluminium ion nonaqueous solution electrolysis liquid, barrier film are completed in glove box, obtain aluminium ion soft-package battery or button cell, i.e.,
Prussian blue and its derivative is the aluminium ion battery of positive pole；
5) battery is assembled, and charge-discharge test is carried out again after standing 12~20h.
The positive electrode of the present invention is Prussian blue and its derivative.The aluminium ion battery preparation technique is simple, price
Cheap, environment-friendly, safety coefficient is high.The aluminium ion battery can be widely applied to portable electric appts, electric automobile, large-scale
The fields such as energy-accumulating power station.
Compared with prior art, the beneficial effects of the invention are as follows：Using Prussian blue and its derivative as positive electrode,
Rafifinal or aluminium-containing alloy as negative material, constitute it is a kind of can discharge and recharge aluminium ion battery.Because the present invention is to positive and negative
Pole material, barrier film, collector and electrolyte etc. have carried out fine selection by experimental study, and combine above-mentioned be previously mentioned
Preparation method, so the present invention is it can be gathered that following features：Propose a kind of novel multivalent ion battery, i.e. aluminium ion cell body
System.Aluminium is reserves most abundant metallic element (82000ppm), significantly larger than lithium (17ppm), sodium (23000ppm), magnesium in the earth's crust
(29000ppm)；The price (U.S. dollars of ≈ 1.4/kilogram) of aluminium is also well below other metals；In addition, property is steady in atmosphere for aluminium
Fixed, this greatly improves the security performance of battery.Prussian blue and its derivative is readily synthesized, and the prices of raw materials are cheap, to ring
Border is friendly, has great application prospect in electrochemical energy storage field.Ionic liquid is electrolysed as a kind of new aluminium ion battery
Liquid, has the advantages that electrochemical window is wide, ionic conductivity is high, without combustibility.It is prepared by aluminium ion battery provided by the present invention
Technique is simple, cheap, environment-friendly, and safety coefficient is high, suitable for large-scale industrialized production, can be widely applied to portable
The fields such as electronic equipment, electric automobile, large-scale energy-accumulating power station.
Brief description of the drawings
Fig. 1 is the cyclic voltammetry curve of ten circles before aluminium ion battery prepared by the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry curve of ten circles before aluminium ion battery prepared by the embodiment of the present invention 2.
Fig. 3 is the charge-discharge test curve of aluminium ion battery first lap prepared by the embodiment of the present invention 2 and the 5th circle.
Embodiment
The present invention is described in more detail below with reference to accompanying drawing.
【Embodiment 1】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.01mol six chloride hydrates
Iron (FeCl3·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Equally weigh 0.005mol
Three hydration six POTASSIUM FERROCYANIDE 99 (K4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K4
[Fe(CN)6] solution.By FeCl3Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed4[Fe(CN)6]
In solution, electric stirring 6h under 60 DEG C of water bath conditions, mixing speed is 250r/min, then naturally cools to room temperature, is centrifuged, and is used
Obtained sample for several times, is placed on vacuum drying chamber and is dried overnight by deionized water and acetone cleaning, and temperature setting is 60 DEG C, secondary
Day, grinding obtains Prussian blue dark blue powder (Fe4[Fe(CN)6]3).The material and conductive agent acetylene black, binding agent is poly- inclined
Difluoroethylene (PVDF) is uniform according to the mixed grindings of 7 ︰ of mass ratio, 2 ︰ 1, is sized mixing, is sufficiently stirred for 1-METHYLPYRROLIDONE (NMP)
Uniformly, it is coated on sizeable stainless (steel) wire (thickness 0.01mm), dries and stay overnight at 80 DEG C of vacuum drying oven, be fabricated to just
Pole pole piece.High-purity aluminium flake is two-sided to be polished with fine sandpaper, is soaked and is dried after 1~2h with ethanol, is cut into sizeable sheet and is made
For negative pole.It is gloves of 1.3 ︰ 1 in ar gas environment in molar ratio by anhydrous Aluminum chloride and 1- ethyl -3- methyl-imidazolium chlorides
Case is configured to aluminium ion battery electrolyte.It regard PE films as barrier film.Finally ready positive pole, negative pole, barrier film and electrolyte
Soft Roll aluminium ion battery is assembled into glove box.Battery is installed after 16h, and charge-discharge test is carried out between 0.05~0.95V.
Its electrochemical process includes a pair of reversible reduction-oxidation peaks it can be seen from Fig. 1 cyclic voltammetry curve, corresponds to respectively
Insertions and abjection of the Al in Prussian blue framework.
【Embodiment 2】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.01mol six chloride hydrates
Iron (FeCl3·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Equally weigh 0.005mol
Hexacyanoferrate potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] molten
Liquid.By FeCl3Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed3[Fe(CN)6] in solution, 40
Electric stirring 6h under DEG C water bath condition, mixing speed is 250r/min, then stands reaction solution to room temperature, centrifugation, spend from
Obtained sample for several times, is placed on vacuum drying chamber and is dried overnight by sub- water and acetone cleaning, and temperature setting is 60 DEG C, next day,
Grinding, obtains the blackish green powder of Berlin green (Fe [Fe (CN)6]).The material and conductive agent acetylene black, binding agent are gathered into inclined difluoro second
Alkene (PVDF) is uniform according to the mixed grindings of 7 ︰ of mass ratio, 2 ︰ 1, is sized mixing, stirred with 1-METHYLPYRROLIDONE (NMP), applies
It is overlying on sizeable stainless (steel) wire (thickness 0.01mm), dries and stay overnight at 80 DEG C of vacuum drying oven, be fabricated to anode pole piece.
High-purity aluminium flake is two-sided to be polished with fine sandpaper, is soaked and is dried after 1~2h with ethanol, is cut into sizeable sheet as negative pole.
Anhydrous Aluminum chloride and 1- ethyl -3- methyl-imidazolium chlorides are configured to for 1.3 ︰ 1 in the glove box of ar gas environment in molar ratio
Aluminium ion battery electrolyte.It regard PE films as barrier film.Finally ready positive pole, negative pole, barrier film and electrolyte in glove box
Inside it is assembled into Soft Roll aluminium ion battery.Battery is installed after 16h, and charge-discharge test is carried out between 0.05~0.95V.Can by Fig. 2
Know, using Prussian blue and its derivative, its first circle specific discharge capacity is 64mA h g for the aluminium ion battery of positive pole-1, the 5th circle
Specific discharge capacity is 35mA h g-1, the material has clearly discharge platform and charging platform, respectively in 0.53V and 0.70V.
From Fig. 3 cyclic voltammogram it can also be seen that, its electrochemical process includes a pair reversible reduction-oxidation peaks, in 0.32V and
0.81V, the discharge platform and charging platform corresponded respectively in electrochemical profiles represents insertions of the Al in material frame and de-
Go out.
【Embodiment 3】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.01mol six chloride hydrates
Nickel (NiCl2·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Equally weigh 0.005mol
Three hydration six POTASSIUM FERROCYANIDE 99 (K4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K4
[Fe(CN)6] solution.By NiCl2Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed4[Fe(CN)6]
In solution, electric stirring 6h under room temperature condition, mixing speed is 250r/min, centrifugation, is cleaned for several times with deionized water and acetone,
Obtained sample is placed on into vacuum drying chamber to be dried overnight, temperature setting is 60 DEG C, next day, grinding obtains grass green powder
(Nix[Fey(CN)6]).By the material and conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) according to the ︰ 1 of 7 ︰ of mass ratio 2
Mixed grinding is uniform, is sized mixing, stirred with 1-METHYLPYRROLIDONE (NMP), is coated on sizeable stainless (steel) wire
Upper (thickness 0.01mm), dries at 80 DEG C of vacuum drying oven and stays overnight, be fabricated to anode pole piece.High-purity aluminium flake is two-sided to be beaten with fine sandpaper
Mill, is soaked with ethanol and is dried after 1~2h, be cut into sizeable sheet as negative pole.By anhydrous Aluminum chloride and 1- ethyls -3-
Methyl-imidazolium chloride is configured to aluminium ion battery electrolyte for 1.3 ︰ 1 in the glove box of ar gas environment in molar ratio.By PE films
It is used as barrier film.Ready positive pole, negative pole, barrier film and electrolyte are finally assembled into Soft Roll aluminium ion battery in glove box.
Battery is installed after 16h, and charge-discharge test is carried out between 0.05~0.95V.
【Embodiment 4】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.01mol six chloride hydrates
Nickel (NiCl2·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Equally weigh 0.005mol
Hexacyanoferrate potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] molten
Liquid.By NiCl2Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed3[Fe(CN)6] in solution, room temperature
Under the conditions of electric stirring 6h, mixing speed is 250r/min, centrifugation, cleaned with deionized water and acetone for several times, by obtained sample
Product are placed on vacuum drying chamber and are dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains brownish-yellow powder (Nix[Fey
(CN)6]).The material is mixed according to the ︰ 1 of 7 ︰ of mass ratio 2 and ground with conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
Mill is uniform, is sized mixing, stirred with 1-METHYLPYRROLIDONE (NMP), is coated on (thickness on sizeable stainless (steel) wire
0.01mm), dry and stay overnight at 80 DEG C of vacuum drying oven, be fabricated to anode pole piece.High-purity aluminium flake is two-sided to be polished with fine sandpaper, uses second
Alcohol soaks dries after 1~2h, is cut into sizeable sheet as negative pole.By anhydrous Aluminum chloride and 1- ethyls -3- methyl-chlorine
Change imidazoles and be configured to aluminium ion battery electrolyte in the glove box of ar gas environment in molar ratio for 1.3 ︰ 1.Using PE films as every
Film.Ready positive pole, negative pole, barrier film and electrolyte are finally assembled into Soft Roll aluminium ion battery in glove box.Battery is filled
After good 16h, charge-discharge test is carried out between 0.05V-0.95V.
【Embodiment 5】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.01mol two chloride hydrates
Copper (CuCl2·2H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L CuCl2Solution；Equally weigh 0.005mol
Hexacyanoferrate potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] molten
Liquid.By K3[Fe(CN)6] solution is slowly added dropwise in CuCl by distribution type peristaltic pump with 1mL/min speed2In solution, room temperature
Under the conditions of electric stirring 6h, mixing speed is 250r/min, centrifugation, cleaned with deionized water and acetone for several times, by obtained sample
Product are placed on vacuum drying chamber and are dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains celadon powder (Cux[Fey
(CN)6]).The material is mixed according to the ︰ 1 of 7 ︰ of mass ratio 2 and ground with conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
Mill is uniform, is sized mixing, stirred with 1-METHYLPYRROLIDONE (NMP), is coated on (thickness on sizeable stainless (steel) wire
0.01mm), dry and stay overnight at 80 DEG C of vacuum drying oven, be fabricated to anode pole piece.High-purity aluminium flake is two-sided to be polished with fine sandpaper, uses second
Dried after alcohol immersion 1-2h, be cut into sizeable sheet as negative pole.By anhydrous Aluminum chloride and 1- ethyls -3- methyl-chlorine
Change imidazoles and be configured to aluminium ion battery electrolyte in the glove box of ar gas environment in molar ratio for 1.3 ︰ 1.Using PE films as every
Film.Ready positive pole, negative pole, barrier film and electrolyte are finally assembled into Soft Roll aluminium ion battery in glove box.Battery is filled
After good 16h, charge-discharge test is carried out between 0.05V-0.95V.
【Embodiment 6】
The aluminium ion cell positive material of the present embodiment is adopted to be made with the following method：Weigh 0.015mol copper acetate (Cu
(OOCCH3)2), it is dissolved in 150mL deionized waters, is configured to 0.1mol/L Cu (OOCCH3)2Solution；Equally weigh 0.01mol
Hexacyanoferrate potassium (K3[Fe(CN)6]), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] molten
Liquid.By K3[Fe(CN)6] solution is slowly added dropwise in Cu (OOCCH by distribution type peristaltic pump with 1mL/min speed3)2Solution
In, electric stirring 6h under room temperature condition, mixing speed is 250r/min, centrifugation, is cleaned with deionized water and acetone for several times, will
To sample be placed on vacuum drying chamber and be dried overnight, temperature setting is 60 DEG C, and next day, grinding obtains celadon powder (Cux[Fey
(CN)6]).The material is mixed according to the ︰ 1 of 7 ︰ of mass ratio 2 and ground with conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
Mill is uniform, is sized mixing, stirred with 1-METHYLPYRROLIDONE (NMP), is coated on (thickness on sizeable stainless (steel) wire
0.01mm), dry and stay overnight at 80 DEG C of vacuum drying oven, be fabricated to anode pole piece.High-purity aluminium flake is two-sided to be polished with fine sandpaper, uses second
Alcohol soaks dries after 1~2h, is cut into sizeable sheet as negative pole.By anhydrous Aluminum chloride and 1- ethyls -3- methyl-chlorine
Change imidazoles and be configured to aluminium ion battery electrolyte in the glove box of ar gas environment in molar ratio for 1.3 ︰ 1.Using PE films as every
Film.Ready positive pole, negative pole, barrier film and electrolyte are finally assembled into Soft Roll aluminium ion battery in glove box.Battery is filled
After good 16h, charge-discharge test is carried out between 0.05~0.95V.
Claims (9)
1. one kind can discharge and recharge aluminium ion battery, it is characterised in that including anode, GND, electrolyte, collector, every
Film；The electrolyte is non-aqueous electrolyte containing aluminium ion, and the collector is the gold for showing electrochemicaUy inert in the electrolytic solution
Belong to paillon foil collector, the barrier film to separate the barrier film of anode and GND, wherein, anode to be Prussian blue and
Its derivative, GND is metallic aluminium or aluminium-containing alloy；
Described Prussian blue and its derivative chemical general formula is：AxM[N(CN)6]y·nH2O, wherein A are alkali metal, selected from K or
One kind in Na；M, N are transition metal, selected from one or both of Fe, Cu, Ni, Co, Mn, Cr.
2. one kind as claimed in claim 1 can discharge and recharge aluminium ion battery, it is characterised in that described Prussian blue and its derivative
Preparation method it is as follows：
1) Prussian blue preparation method：It is Prussian blue to be obtained by simple liquid phase method, weigh 0.01mol six chloride hydrates
Iron (FeCl3·6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Equally weigh 0.005mol
Three hydration six POTASSIUM FERROCYANIDE 99 (K4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K4
[Fe(CN)6] solution.By FeCl3Solution is added dropwise in K by distribution type peristaltic pump with 1mL/min speed4[Fe(CN)6] solution
In, electric stirring 6h under 60 DEG C of water bath conditions, mixing speed is 250r/min, then naturally cools to room temperature, centrifugation, spend from
Obtained sample for several times, is placed on vacuum drying chamber and is dried overnight by sub- water and acetone cleaning, and temperature setting is 60 DEG C, next day,
Grinding, obtains Prussian blue dark blue powder (Fe4[Fe(CN)6]3)。
2) preparation method of Prussian blue analog derivative：
(1) preparation of Berlin green：Berlin green can also be prepared by liquid phase method, weigh 0.01mol ferric chloride hexahydrate (FeCl3·
6H2O), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L FeCl3Solution；Six cyanogen for equally weighing 0.005mol close iron
Sour potassium (K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By FeCl3It is molten
Liquid is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed3[Fe(CN)6] in solution, under 40 DEG C of water bath conditions
Electric stirring 6h, mixing speed is 250r/min, then stands reaction solution to room temperature, centrifugation, clear with deionized water and acetone
Wash for several times, obtained sample is placed on into vacuum drying chamber is dried overnight, temperature setting is 60 DEG C, next day, grinding obtains Berlin green
Blackish green powder (Fe [Fe (CN)6])；
(2) grass green powder (Nix[Fey(CN)6]) preparation：Weigh 0.01mol Nickel dichloride hexahydrate (NiCl2·6H2O),
It is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Three six cyanogen of hydration for equally weighing 0.005mol are sub-
Potassium ferrite (K4[Fe(CN)6]·3H2O), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K4[Fe(CN)6] solution.Will
NiCl2Solution is slowly added dropwise in K by distribution type peristaltic pump with 1mL/min speed4[Fe(CN)6] in solution, under room temperature condition
Electric stirring 6h, mixing speed is 250r/min, centrifugation, is cleaned with deionized water and acetone for several times, obtained sample is placed
It is dried overnight in vacuum drying chamber, temperature setting is 60 DEG C, next day, grinding obtains grass green powder (Nix[Fey(CN)6])；
(3) brownish-yellow powder (Nix[Fey(CN)6]) preparation：Weigh 0.01mol Nickel dichloride hexahydrate (NiCl2·6H2O),
It is dissolved in 100mL deionized waters, is configured to 0.1mol/L NiCl2Solution；Equally weigh 0.005mol Hexacyanoferrate potassium
(K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By NiCl2Solution leads to
Distribution type peristaltic pump is crossed to be slowly added dropwise in K with 1mL/min speed3[Fe(CN)6] in solution, electric stirring 6h under room temperature condition,
Mixing speed is 250r/min, centrifugation, is cleaned with deionized water and acetone for several times, obtained sample is placed on into vacuum drying chamber
It is dried overnight, temperature setting is 60 DEG C, next day, grinding obtains brownish-yellow powder (Nix[Fey(CN)6])；
(4) celadon powder (Cux[Fey(CN)6]) preparation：Weigh 0.01mol Copper dichloride dihydrate (CuCl2·2H2O),
It is dissolved in 100mL deionized waters, is configured to 0.1mol/L CuCl2Solution；Equally weigh 0.005mol Hexacyanoferrate potassium
(K3[Fe(CN)6]), it is dissolved in 50mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By K3[Fe(CN)6]
Solution is slowly added dropwise in CuCl by distribution type peristaltic pump with 1mL/min speed2In solution, electric stirring under room temperature condition
6h, mixing speed is 250r/min, centrifugation, is cleaned with deionized water and acetone for several times, obtained sample is placed on into vacuum and done
Dry case is dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains celadon powder (Cux[Fey(CN)6])；
(5) celadon powder (Cux[Fey(CN)6]) preparation：Weigh 0.015mol copper acetate (Cu (OOCCH3)2), it is dissolved in
In 150mL deionized waters, 0.1mol/L Cu (OOCCH are configured to3)2Solution；Equally weigh 0.01mol Hexacyanoferrate potassium
(K3[Fe(CN)6]), it is dissolved in 100mL deionized waters, is configured to 0.1mol/L K3[Fe(CN)6] solution.By K3[Fe(CN)6]
Solution is slowly added dropwise in Cu (OOCCH by distribution type peristaltic pump with 1mL/min speed3)2It is electronic under room temperature condition in solution
6h is stirred, mixing speed is 250r/min, centrifugation is cleaned for several times with deionized water and acetone, obtained sample is placed on very
Empty drying box is dried overnight, and temperature setting is 60 DEG C, and next day, grinding obtains celadon powder (Cux[Fey(CN)6])。
3. one kind as claimed in claim 1 can discharge and recharge aluminium ion battery, it is characterised in that the cell negative electrode material is purity
The alloy that metallic aluminium or metallic aluminium more than 90% are formed with copper, silver, nickel, lead, tin, bismuth, iron.
4. one kind as claimed in claim 1 can discharge and recharge aluminium ion battery, it is characterised in that described containing the non-water system electrolysis of aluminium ion
Liquid includes aluminum halide and ionic liquid, and the mol ratio of the aluminum halide and ionic liquid is (1.1~2) ︰ 1.
5. one kind as claimed in claim 4 can discharge and recharge aluminium ion battery, it is characterised in that the anion bag of the ionic liquid
Include Cl-, Br-, I-, PF6 -, BF6 -, CN-, SCN-, [N (CF3SO2)2]-Or [N (CN)2]-Ion.
6. one kind as claimed in claim 4 can discharge and recharge aluminium ion battery, it is characterised in that the cation include imidazoles from
Son, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium ion, quaternary ammonium salt ion, quaternary phosphonium salt ion or tertiary sulfosalt
Ion.
7. one kind as claimed in claim 1 can discharge and recharge aluminium ion battery, it is characterised in that the metal foil of the electrochemicaUy inert
Piece collector includes tantalum piece, niobium sheet, molybdenum sheet, titanium sheet, stainless steel substrates, gold and platinum group metal.
8. one kind as claimed in claim 1 can discharge and recharge aluminium ion battery, it is characterised in that the separation anode and battery
The diaphragm material of negative pole includes but is not limited to：TPO such as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
9. as claimed in claim 1 can discharge and recharge aluminium ion battery preparation method, it is characterised in that comprise the following steps：
1) Prussian blue and its derivative, conductive material, binding agent are proportionally weighed into mixing respectively, active material slurry is made
Material is applied on inert metal collector, is dried in 60~100 DEG C, and thickness is made for 0.5~2mm sheet anode composite materials
Material；
2) by the metal aluminum or aluminum alloy that thickness is 0.1~1mm, polish two-sided, after washes of absolute alcohol, dry, that is, obtain
Cell negative electrode material；
3) ionic liquid is dried into 12h at 80~150 DEG C of vacuum drying chamber, subsequent aluminum halide and ionic liquid using mol ratio as
(1.1~2) ︰ 1 are mixed in the glove box of ar gas environment, magnetic agitation 0.5h, that is, are configured to containing can move freely aluminium ion
Nonaqueous solution electrolysis liquid；
4) by step 1) obtained cell positive material, step 2) obtain cell negative electrode material, step 3) obtain containing aluminium from
Sub- nonaqueous solution electrolysis liquid, barrier film are completed in glove box, obtain aluminium ion soft-package battery or button cell, i.e., general Shandong
The aluminium ion battery that scholar is blue and its derivative is positive pole；
5) battery is assembled, and charge-discharge test is carried out again after standing 12~20h.
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