CN105609754B - A kind of double positive electrodes and aqoue seconary battery - Google Patents
A kind of double positive electrodes and aqoue seconary battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to a kind of double positive electrodes and aqoue seconary batteries, the active material of double positive electrodes is simultaneously from anode and electrolyte, anode includes positive electrode active materials, positive electrode active materials for can deintercalation divalent zinc ion compound, electrolyte includes electrolyte and solvent, electrolyte includes soluble zinc salt and soluble manganese salt, and solvent is water.When the charging voltage of double positive electrodes is in 1.8V (vs.Zn/Zn2+) more than when, while zinc ion, manganese ion in electrolyte act synergistically, electrochemical oxidation-reduction process occurs for manganese ion, realizes the high specific capacity of positive electrode and cyclical stability so that the capacity of double positive electrodes is in 200 mAh g‑1More than, and at low cost, long lifespan, can fast charging and discharging, the outstanding features such as environmental-friendly, as aqoue seconary battery positive electrode, have a extensive future.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of double positive electrodes and aqoue seconary battery.
Background technology
Today's society, fossil energy insufficient supply have become the bottleneck of global economic development.Meanwhile it is made using fossil energy
Into environmental pollution has become increasingly serious, active development utilize renewable new energy and scale electric power storage technology, build intelligent grid, be
The mankind are reduced to the dependence of fossil energy and the only way of environment purification.Chemical electric power storage technology based on battery is that realization can be again
The premise and basis of raw energy power generation, is in urgent need.Existing chemical energy storage battery mainly have lead-acid battery, Ni-MH battery,
Lithium ion battery of flow battery and organic media etc..But scale energy storage proposes more battery in terms of service life, security, cost
High request, existing battery technology, which is difficult to fully meet, it is necessary to develop, meets its desired battery new technology.
Electrode material and electrolyte play battery performance conclusive effect.Manganese-base oxide-manganese dioxide is due to coming
Source enriches, is inexpensive, electrode potential is higher and is widely studied the positive electrode as battery.The energy storage mechnism of manganese dioxide is main
Manganese (IV) is relied on to reversible oxidation-reduction reaction between manganese (III) to store charge, theoretical specific capacity is reachable
308mAh/g, but manganese dioxide actual specific capacity prepared by the prior art is much smaller than theoretical value.Since two thousand nine, Tsing-Hua University is big
Kang Fei spaces seminar has applied for that the serial water system based on manganese dioxide positive pole can fill Zinc ion battery, patent CN
In 101783419 A, using Mn oxide as positive electrode active materials, using zinc as negative electrode active material, with the aqueous solution containing zinc ion
For electrolyte, the secondary cell in neutral aqueous solution is formed, due to insertion-abjection of zinc ion, MnO2Positive electrode specific capacity is reachable
200-300mAh/g is close with theoretical value.In patent CN102013526A, anode employs the dioxy of doped metallic elements
Change manganese material；In patent CN 102097662A, a certain amount of TiO is with the addition of in manganese dioxide positive pole material2Or titanate.It is special
It is not that the seminar applied for a kind of zinc ion rechargeable battery and its manufacturing method (CN104272523A), just in 2014
Pole active material uses carbon based manganese dioxide composite material, and the carbon based manganese dioxide refers to manganese dioxide preparation process Central Plains
Position adds in carbon material, makes to adhere to upper manganese dioxide on the surface of carbon material carrier, so as to improve the large current characteristic of material and
The cycle life of battery, and positive electrode specific capacity is higher than 1000mAh/g, considerably beyond theoretical specific capacity.It removes and contains in electrolyte
Outside zinc ion, manganese ion is also added, applicant thinks that increased divalent manganesetion and carbon based manganese dioxide are compound in electrolyte
Material concerted reaction adds the capacity of battery.In addition, the seminar thinks that manganese dioxide (is abbreviated as MnO2) there is big ruler
Very little Open architecture, cation (such as zinc ion, manganese ion in tunnel）It can be handed over the cation in aqueous solution
It changes, in ion exchange process, these tunnel structures can keep stablizing and obtaining higher specific capacity.Dioxy is carried in order to illustrate carbon
Change the synergistic effect of manganese composite material and the manganese ion in electrolyte, which provides embodiment 2 as a comparison, from implementation
Example 2 understands, the positive active material of the second battery is manganese dioxide, the ZnSO4 containing 1mol/L and 0.5 mol/L in electrolyte
MnSO4, and the capacity of second battery is only 200mAh/g；3rd battery carries manganese dioxide electrode piece as just using graphene
Pole, electrolyte 1mol/LZnSO4Aqueous solution, and the capacity of the 3rd battery can accomplish 260mAh/g;Positive-active is proved with this
Material must use carbon based manganese dioxide composite material.
The content of the invention
We have discovered that even if there is insertion-abjection of divalent zinc ion, the specific volume of manganese dioxide electrode can not be caused
Amount is higher by its theoretical value.Only at the same time containing zinc, manganese ion aqueous solution in, it is under the synergistic effect of manganese ion and higher
The process of electrochemical oxidation-reduction occurs for divalent manganesetion in solution under current potential, and a small amount of Mn oxide constantly deposits inhibition and lives
The solution loss of property substance, insertion-abjection of the zinc ion in manganese dioxide electrode at this time could obtain high capacity and height is steady
It is qualitative.When manganese dioxide specific capacity is far above its theoretical specific capacity, activity may be made since manganese ion constantly aoxidizes electro-deposition
Photosynthetic matter accumulation as a result, not significantly improve the specific discharge capacity of itself.And zinc ion insertion-abjection can occur
Electrode material is not limited to MnO2.That is, divalent manganesetion plays key effect, existing inhibition electrode in electrolyte
The effect of capacity attenuation provides active material and capacity again.For this purpose, the present invention proposes a kind of double anode materials of aqoue seconary battery
The concept of material.The electro-chemical activity of this pair of positive electrode is simultaneously from solid electrode and its electrolyte, the activity of solid electrode
Substance is that can take off-the compound of embedding zinc, lithium or sodium ion；Electrolyte be solute based on zinc ion and manganese ion salt, water is molten
Agent simultaneously has the liquid of ionic conductivity or gel state material.Utilize the embedding of the lower zinc ion of manganese ion synergistic effect in electrolyte
Enter-deviate from the attenuation for inhibiting capacity with manganese ion electrochemical oxidation-reduction process, obtain high specific capacity, realize electrode
High cyclical stability.The method can significantly increase the capacity and cycle life of aqoue seconary battery positive electrode, and green
It is environmentally friendly, simple and easy to do.
It is an object of the invention to be directed to capacity attenuation in inexpensive manganese oxide anode charge and discharge process to be difficult to what is inhibited
Bottleneck problem proposes a kind of double positive electrodes suitable for aqoue seconary battery.Collaboration using zinc, manganese ion in electrolyte is made
With with manganese ion electrochemical oxidation-reduction process, realize positive electrode high capacity and cyclical stability, and positive electrode
Be not limited to manganese bioxide material, the positive electrode have capacity is high, the at low cost, long-life, can fast charging and discharging, environmental-friendly
Etc. outstanding features.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of double positive electrodes, the active material of double positive electrodes are described simultaneously from anode and electrolyte
Anode include positive electrode active materials, the positive electrode active materials for can deintercalation divalent zinc ion compound, the electricity
Solving liquid includes electrolyte and solvent, and the electrolyte includes soluble zinc salt and soluble manganese salt, and the solvent is water, when
The charging voltage of double positive electrodes is in 1.8V (vs.Zn/Zn2+) more than when, zinc ion, manganese in the electrolyte from
While son acts synergistically, electrochemical oxidation-reduction process occurs for the manganese ion so that double anode materials
The capacity of material is in 200 mAh g-1More than.
Preferably, the positive electrode active materials is can deintercalation zinc ion, lithium ion, the compounds of sodium ion.
Preferably, the positive electrode active materials are selected from LiMn2O4、LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiNiO2、
LiMnPO4、Na0.44MnO2, in metal oxide and above-claimed cpd in the material containing other metallic elements M doping one
Kind or more than one, other metallic elements M be selected from Li, Na, Mg, Fe, Ca, Ba, V, Pb, Bi, Cr, Al, Ti, Co,
One or more in Mn, Ni, Zn, Nb, Cu, La.
Preferably, the anode includes plus plate current-collecting body, the cathode film being formed on the plus plate current-collecting body, by institute
The weight for the cathode film stated is 100% meter, the cathode film by 30% ~ 88% the positive electrode active materials, 10% ~ 50%
Conductive agent and 2% ~ 20% adhesive composition.
It is further preferred that the anode is to be coated in plus plate current-collecting body by the way that the cathode film is mixed slurry
On, then suppress.
It is further preferred that the conductive agent is selected from graphite, graphene, carbon black, acetylene black, Carbon fibe, nano-sized carbon
The combination of one or more of fiber, carbon nanotube；The binding agent is selected from polytetrafluoroethylene (PTFE), water-soluble rubber, gathers
The combination of one or more of inclined tetrafluoroethene, cellulose；The plus plate current-collecting body is selected from titanium net, covers carbon titanium net, no
Rust steel mesh covers carbon stainless steel net, covers conductive plastics stainless (steel) wire, punching stainless steel foil or cuts drawing titanium net.
Preferably, content of the soluble zinc salt in the electrolyte is 0.2~3 mol/L, and described can
Content of the dissolubility manganese salt in the electrolyte is 0.05 ~ 3 mol/L.
Preferably, the pH value of the electrolyte is 3~9, and in liquid or gel state with ionic conductivity.
Preferably, the electrolyte further includes cationic salt form supporting electrolyte, and the cationic salt form supports electricity
The one kind of Xie Zhiwei in lithium salts, magnesium salts, calcium salt, strontium salt, sodium salt, sylvite, rubidium salt, cesium salt, cobalt salt, nickel salt, mantoquita, aluminium salt
Or several combinations, the additive amount of the cationic salt form supporting electrolyte are the 1% ~ 50% of the electrolyte gross mass.
Preferably, the electrolyte further includes corrosion inhibition additive, the corrosion inhibition additive be selected from gallium salt, indium salts,
Cadmium salt, polyethylene glycol, cetyl trimethylammonium bromide, tetrabutylammonium bromide, gelatin, ethylenediamine, amion acetic acid, ammonia oxalic acid
One or more of combination, the additive amount of the corrosion inhibition additive account for the electrolyte gross mass 0.01~
20%.
A kind of aqoue seconary battery, including double positive electrodes, can be mutually steady with the electrolyte intermediate ion
The fixed cathode existed and self discharge reaction does not occur, the cathode are zinc load.
Zinc ion and manganese ion have very special synergistic effect in electrolyte of the present invention, are incited somebody to action when the two exists simultaneously
It steps up the capacity of positive electrode and with high stability and reversibility, and whether contains element in positive electrode active materials
Manganese relation is little.When this synergistic effect shows as individually containing zinc ion or manganese ion in electrolyte, electrode shows as double electricity
The pseudo-capacitance feature of layer capacitance or surface oxidation-reduction reaction, electrode specific capacity is low, and capacity attenuation is rapid, poorly reversible.
And the two, when existing simultaneously, electrode shows the synergistic effect of zinc, manganese ion, and this synergistic effect is shown as：Low voltage (<
1.8V vs.Zn/Zn2+) under, zinc ion can steadily be embedded in-deviate from, and cyclical stability is improved；High voltage (>1.8V
vs.Zn/Zn2+) under, electrochemical oxidation-reduction also occurs in addition to playing the role of stabilized electrodes structure for the divalent manganesetion in solution
Reaction process:
Mn2+↔MnOOH+e
MnOOH↔Mn2++ MnO2+ e
Positive electrode surface refines due to the continuous deposition of Mn oxide, and reactivity area constantly increases therewith, so as to zinc from
Insertion-abjection of son extends to body phase by surface reaction, therefore electrode capacity constantly increases.As long as it importantly, charges
Reaction terminated in before generation analysis oxygen side reaction, the coulombic efficiency of this pair of anode discharge and recharge reaction can remain at 95% with
On, and capacity gradually increases.
Due to using the technology described above, there are following advantages compared with prior art by the present invention：
Beneficial effects of the present invention：Use can deintercalation divalent zinc ion compound for anode, electrolyte can be only containing can
Soluble zinc salt and manganese salt；Also soluble zinc salt and manganese salt can be contained, and add in supporting electrolyte；Or containing soluble zinc salt and
Manganese salt adds in supporting electrolyte and corrosion inhibiter.Pass through zinc, the synergistic effect of manganese ion and manganese ion electrochemistry oxygen in electrolyte
Change-reduction process realizes positive electrode active materials based on solid electrode, supplemented by manganese active ion in electrolyte it is double just
Pole concept.This pair of anode material discharging voltage is in 1.3V (vs.Zn/Zn2+) more than, have capacity is high, the at low cost, long-life, can
The outstanding features such as fast charging and discharging, environmental-friendly, as aqoue seconary battery positive electrode, have a extensive future.
Description of the drawings
Fig. 1 be battery Cell 1 obtained under 100mA/g current densities for the first time, the 10th time and the 20th time cycle charge and discharge
Electric curve, wherein, ordinate：Cell voltage/V；Abscissa：Specific capacity/mAh g-1；
Fig. 2 is cycle performances of the battery Cell 1 obtained under 100mA/g current densities, wherein, ordinate 1：Electric discharge
Capacity/mAh g-1；Ordinate 2：Coulombic efficiency/%;Abscissa：Cycle-index；
Fig. 3 is charging and discharging curves of the battery Cell2 obtained under 100mA/g current densities, wherein, ordinate：Battery
Voltage/V；Abscissa：Specific capacity/mAh g-1；
Fig. 4 is typical charging and discharging curves of the battery Cell 3 obtained under 100mA/g current densities, wherein, ordinate：
Cell voltage/V；Abscissa：Specific capacity/mAh g-1；
Fig. 5 is typical charging and discharging curves of the battery Cell 4 obtained under 100mA/g current densities, wherein, ordinate：
Cell voltage/V；Abscissa：Specific capacity/mAh g-1。
Specific embodiment
Following embodiment is described in further detail for aqoue seconary battery with double positive electrodes.
Embodiment 1
Na：The molar ratio of Mn is 0.55:1, sodium carbonate（0.055mol）It is raw material with manganese carbonate (0.1mol), ball milling is common
It is mixed, it is put into ceramic boat, in Muffle furnace, 5 DEG C of min-1It is warming up to 500 DEG C of constant temperature 2h, then 2 DEG C of min-1It is warming up to 800
DEG C sintering 16h obtain Na0.44MnO2.By the Na of above-mentioned synthesis0.44MnO2As the active material of electrode, according to active material：Second
Acetylene black：Adhesive polytetrafluoroethylene (PTFE) is 85:10:5 ratio mixing, rolls and is pressed into piece, when drying 12 is small in 120 DEG C of baking ovens, cuts out
Into 1 × 1cm2, active material loading about 5mg/cm2Left and right, is pressed on stainless (steel) wire with the pressure of 10MPa on hydraulic press and made
Into electrode.Na0.44MnO2Electrode is as anode, and using the big excessive zinc metal sheet of active material as cathode, electrolyte is 0.5 mol L- 1ZnSO4+1mol L-1Na2SO4+0.05 mol L-1MnSO4 mixed aqueous solutions are assembled into battery, are denoted as the 1st battery
Cell1.1st battery Cell1 is in 100mA g-1(with positive active material Mass Calculation specific capacity and charging and discharging currents density)
The 1st time, the 10th time and the 20th time typical charge and discharge curve under constant current is as shown in Figure 1, its cycle performance is as shown in Figure 2.With just
Pole active material Mass Calculation, the capacity after 1 charge and discharge of the 1st battery Cell 100 times reach 278 mAh g-1。
Embodiment 2
Using commercial LiMn2O4As the active material of electrode, according to active material：Acetylene black：Adhesive is 85:10:
5 ratio mixing, rolls and is pressed into piece, when drying 12 is small in 120 DEG C of baking ovens, be cut into 1 × 1cm2, active material loading about 5mg/
cm2Left and right, is pressed on stainless (steel) wire with the pressure of 10MPa on hydraulic press and electrode is made.LiMn2O4Electrode is as anode, with zinc
Piece is cathode, and electrolyte is 1mol L-1Li2SO4+0.5 mol L-1ZnSO4+0.05 mol L-1MnSO4 mixing is water-soluble
Liquid is assembled into battery, is denoted as the 2nd battery Cell2.2nd battery Cell2 is in 100mA g-1(in terms of positive active material quality
Calculate specific capacity and charging and discharging currents density) charge and discharge curve under constant current is as shown in Fig. 3.In terms of positive active material quality
It calculates, the capacity of the 2nd battery Cell2 can accomplish 300 mAh g-1More than.
Comparative example 1
Prepare 0.17mol/L KMnO4Solution separately takes liquid Mn (NO3)2(wt50%), by 2:3（Molar ratio）With 2mL/min
Speed, be added dropwise to KMnO in alkaline conditions4In solution, pH value that reaction process is shown according to acidometer passes through addition
0.1mol/L NH3·H2O adjusts pH=10.5, strong stirring 12h.Precipitation is centrifugally separating to obtain, with deionized water and absolute ethyl alcohol
Washing, in 70 DEG C of constant pressure and dry, that is, MnO2。
By the MnO of above-mentioned synthesis2As the active material of electrode, according to active material：Acetylene black：Adhesive is 80:10:
10 ratio mixing, rolls and is pressed into piece, when drying 12 is small in 120 DEG C of baking ovens, be cut into 1 × 1cm2, active material loading is about
5.4mg/cm2Left and right, is pressed on stainless (steel) wire with the pressure of 10MPa on hydraulic press and electrode is made.MnO2Electrode as anode,
Using zinc metal sheet as cathode（Cathode preparation method is the same as embodiment 1）, electrolyte is 0.5 mol L-1ZnSO4 adds 1mol L-1Na2SO4
Aqueous solution is assembled into battery, is denoted as the 3rd battery Cell3.3rd battery Cell3 is in 100 mA g-1(with positive active material matter
Amount calculates specific capacity and charging and discharging currents density) typical charge and discharge curve under constant current is as shown in Fig. 4.With positive electrode active material
Matter Mass Calculation, the capacity of the 3rd battery Cell3 is only 21 mAh g-1。
Comparative example 2
Na：The molar ratio of Mn is 0.55:1, sodium carbonate（0.055mol）It is raw material with manganese carbonate (0.1mol), ball milling is common
It is mixed, it is put into ceramic boat, in Muffle furnace, 5 DEG C of min-1It is warming up to 500 DEG C of constant temperature 2h, then 2 DEG C of min-1It is warming up to 800
DEG C sintering 16h obtain Na0.44MnO2.By the Na of above-mentioned synthesis0.44MnO2As the active material of electrode, according to active material：Second
Acetylene black：Adhesive is 80:10:10 ratio mixing, rolls and is pressed into piece, when drying 12 is small in 120 DEG C of baking ovens, be cut into 1 × 1cm2,
Active material loading about 5mg/cm2Left and right, is pressed on stainless (steel) wire with the pressure of 10MPa on hydraulic press and electrode is made.
Na0.44MnO2Electrode is as anode, and using zinc metal sheet as cathode, electrolyte is 1mol L-1Na2SO4 adds 0.05 mol L-1MnSO4 water
Solution is assembled into battery, is denoted as the 4th battery Cell4.4th battery Cell4 is in 100mA g-1(with positive active material quality
Calculate specific capacity and charging and discharging currents density) under constant current through overcharging the charging and discharging curve of process as shown in Fig. 5.With anode
Active material Mass Calculation, the capacity of the 4th battery Cell4 can accomplish 87 mAh g-1。
Comparative example 3
It is as follows that carbon nanotubes carries manganese dioxide preparation method：0.6 gram of carbon nanotubes is added in 300 milliliters 0.1 mole every liter
Manganese acetate aqueous solution in be sufficiently stirred, carbon nanotubes is allowed to be uniformly dispersed, after 200mL0.1 moles every liter of potassium permanganate water
Solution is added in acetic acid manganese solution, when stirring 10 is small so that and manganese dioxide is fully deposited and adhered on the surface of carbon nanotubes,
Then filtering precipitate, and be washed with deionized, drying carbon nanotubes carries manganese dioxide.
It is 8 in mass ratio that carbon nanotubes, which is carried manganese dioxide powder, conductive agent carbon black and binding agent to gather inclined tetrafluoroethene,:1:
Coated on stainless steel foil after 1 mixing, a certain size is cut into, drying is carbon nanotubes load manganese dioxide electrode in vacuum
Piece.Manganese dioxide electrode piece is carried as anode using carbon nanotubes obtained, using the zinc paper tinsel of 0.1mm thickness as cathode, electrolyte is 1 mole
Every liter of zinc sulfate and 0.5 mole every liter of manganese sulfate solution composition battery, are denoted as the 5th battery Cell5.With positive electrode active material
Matter Mass Calculation, the capacity of the 5th battery Cell5 can accomplish 240 mAh g-1.Although in the embodiment 3 of CN201480000469.3
The capacity for recording battery made from this method is 1935.7 mAh g-1, still, through the present inventor the study found that in the patent
Capacity is recorded wrong.Because electrolyte used in patent contains divalent manganesetion, when charging voltage is more than 1.8V (vs.Zn/Zn2+)
When, oxide deposition reaction generation MnO easily occurs for divalent manganesetion2.The MnO of new deposition generation2Adhere on the electrode, both effectively
The attenuation of capacity is inhibited, and increases capacity.That is, carbon nanotubes carries the capacity of manganese dioxide electrode not only from electricity
There is the contribution of manganese ion oxide deposition in electrolyte, the characteristics of meeting " double anodes ", so high in the patent in pole in itself
Specific capacity is not solid MnO2The actual specific capacity value of electrode in itself.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously carried out, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes according to the present invention
The equivalent change or modification of work should all cover within the scope of the present invention.
Claims (6)
1. a kind of aqoue seconary battery, it is characterised in that：The aqoue seconary battery includes double positive electrodes, it is described it is double just
The active material of pole material includes positive electrode active materials, the anode simultaneously from anode and electrolyte, the anode
Active material for can deintercalation divalent zinc ion compound, the electrolyte include electrolyte and solvent, the electrolyte
Including soluble zinc salt and soluble manganese salt, the solvent is water, when double positive electrodes are in vs.Zn/Zn2+Lower charging
Voltage is in more than 1.8V, while zinc ion, manganese ion in the electrolyte act synergistically, the manganese ion
Generation electrochemical oxidation-reduction process so that the capacity of double positive electrodes is in 200 mAh g-1More than；It is described just
Pole active material is selected from LiMn2O4、LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiNiO2、LiMnPO4、Na0.44MnO2, Yi Jishang
The one or more in the material containing other metallic elements M doping in compound are stated, other metallic elements M is
One or more in Li, Na, Mg, Fe, Ca, Ba, V, Pb, Bi, Cr, Al, Ti, Co, Mn, Ni, Zn, Nb, Cu, La, institute
The anode stated includes plus plate current-collecting body, the cathode film being formed on the plus plate current-collecting body, by the weight of the cathode film
For 100% meter, the cathode film is by 30% ~ 88% positive electrode active materials, 10% ~ 50% conductive agent and 2% ~ 20%
Adhesive forms；The electrolyte further includes cationic salt form supporting electrolyte, the cationic salt form supporting electrolyte
For one kind or several in lithium salts, magnesium salts, calcium salt, strontium salt, sodium salt, sylvite, rubidium salt, cesium salt, cobalt salt, nickel salt, mantoquita, aluminium salt
The combination of kind, the additive amount of the cationic salt form supporting electrolyte are the 1% ~ 50% of the electrolyte gross mass.
2. aqoue seconary battery according to claim 1, it is characterised in that：The conductive agent is selected from graphite, graphite
The combination of one or more of alkene, carbon black, carbon fiber, carbon nanotubes；The adhesive is selected from polytetrafluoroethylene (PTFE), water-soluble
Property rubber, gather the combination of inclined tetrafluoroethene, one or more of cellulose；The plus plate current-collecting body is selected from titanium net, covers
Carbon titanium net, stainless (steel) wire cover carbon stainless steel net, cover conductive plastics stainless (steel) wire or punching stainless steel foil.
3. aqoue seconary battery according to claim 1, it is characterised in that：The soluble zinc salt is in the electrolysis
Content in liquid is 0.2~3 mol/L, content of the soluble manganese salt in the electrolyte for 0.05 ~ 3 mole/
It rises.
4. aqoue seconary battery according to claim 1, it is characterised in that：The pH value of the electrolyte is 3~9, and
In liquid or gel state with ionic conductivity.
5. aqoue seconary battery according to claim 1, it is characterised in that：The electrolyte further includes inhibition addition
Agent, the corrosion inhibition additive are selected from gallium salt, indium salts, cadmium salt, polyethylene glycol, cetyl trimethylammonium bromide, the tetrabutyl
The combination of one or more of ammonium bromide, gelatin, ethylenediamine, amion acetic acid, ammonia oxalic acid, the corrosion inhibition additive add
Dosage accounts for the 0.01~20% of the electrolyte gross mass.
6. aqoue seconary battery according to claim 1, it is characterised in that：The aqoue seconary battery further includes can
It is mutually stabilized with the electrolyte intermediate ion and the cathode of self discharge reaction does not occur, the cathode is zinc load.
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