CN109980302A - A kind of water system Zinc ion battery colloidal electrolyte and its preparation method and application - Google Patents
A kind of water system Zinc ion battery colloidal electrolyte and its preparation method and application Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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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
The invention discloses a kind of water system Zinc ion battery colloidal electrolyte and its preparation method and application, which is to be added in liquid electrolyte uniformly mixing by clay material to constitute.Preparation method is that clay material is added to conventional liquid electrolyte, is sufficiently mixed under stirring, by ageing, obtains the colloidal electrolyte of stable homogeneous.Colloidal electrolyte prepared by the invention has higher ionic conductivity than liquid electrolyte, colloid Zinc ion battery is had excellent performance, safety and performance are stablized, higher specific capacity plays, excellent cyclical stability, shelving performance etc. are kept under high/low currents density, the water system zinc ion energy storage technology requirement for meeting high-energy density, long-life, has wide application development space.
Description
Technical field
The invention belongs to water system Zinc ion battery field, it is related to a kind of water system Zinc ion battery colloidal electrolyte material and system
Preparation Method and application.
Background technique
Lithium ion battery is produced in portable electronic as a kind of electrochemical energy storing device for occupying social leading position
Good application prospect is achieved in product, electric car.However, since the scarcity of metal lithium resource causes lithium ion battery high
The factors such as cost presence, the large-scale application of lithium ion battery is faced with acid test.Zinc ion battery, be after
The novel high security energy-storage battery system of lithium ion battery latter, its used metal zinc load, aqueous electrolyte have
Peculiar high safety, low toxicity and chemical inertness.Chargeable aqueous Zinc ion battery is even more to have the characteristics that avirulent, and zinc exists
The abundance in the whole world is higher, provides a kind of inexpensive, high security selection for following electrochemical energy storage.Therefore it is used as respectively
The anode of kind chargeable water system battery, such as zinc-nickel, zinc metal oxide, zinc complex, zinc and air cell and Zinc ion battery, although
Water system zinc battery has many advantages, but the problem of due to battery system and zinc metal, is recycled water system Zinc ion battery also not
Commercialization can be not achieved.Zinc metal in aqueous solution charge and discharge when the problems such as being frequently accompanied by electrode deformation, dendrite, burn into liberation of hydrogen,
Lead to deterioration of cell properties, occurs actually making such as the problems such as cycle life is short, self discharge is more serious, circulation volume decline is fast
Be quickly invalidated with battery in the process, be not able to satisfy actual demand, this be also such water system battery fail to obtain it is widely applied heavy
Want reason.Secondly, traditional Zinc ion battery uses liquid electrolyte, contain a large amount of active water in liquid electrolyte, water can add
Corrosion of the speed to electrode, water decomposition will lead to the raising of battery charging and discharging specific capacity falseness, and unstable, if electrolyte can be allowed
Middle water content reduces and cell electrolyte is made to have good ion selectivity, thus zinc ion can be inhibited uneven
Deposition forms zinc dendrite, and enhances the charge and discharge Reversible Cycle of battery.
For this purpose, be attempted to solve the problems, such as that this kind of battery exists from electrode modification and the modified angle of electrolyte, it is many
It is more similar to anode, cathode study on the modification Comparision, electrolyte study on the modification is also gradually risen in recent years, is studied relatively more
Work concentrate on electrolysis additive, gel electrolyte and all solid state electrolyte direction.Colloidal electrolyte is a kind of novel
Soft material electrolyte, the lithium ion colloidal electrolyte of existing report is received by dispersing suitable ceramics in nonaqueous electrolyte
Rice material, colloidal electrolyte is introduced into electrode for lithium secondary cell material, can express good electrochemical stability.And
Water system lead-acid battery uses SiO2、Al2O3Material has formed good market application.In short, existing colloidal electrolyte, greatly
Mostly use inertia nano ceramic material (such as SiO2、Al2O3) be added liquid electrolyte in obtain, such as Chinese invention patent
CN201510431032.1 uses inertia SiO2As colloidal electrolyte material, the colloidal electrolyte of high concentration to a certain extent
It greatly suppresses because liquid electrolyte is using bring side reaction, improves circulating battery stability.But the inertia material of high concentration
Material introduces and inevitably results in the low ionic conductivity of electrolyte, and battery polarization is caused to increase, therefore often it can be seen that similar special
Benefit is all that a small amount of ceramic material is added to prepare colloidal electrolyte, this will inhibit significantly the performance of colloidal electrolyte to play and apply
Limitation.For this purpose, the present invention proposes a kind of electrolyte of superelevation ion conductor, not only with the excellent spy of colloidal electrolyte
Property, and prepared colloidal electrolyte conductivity exceeds liquid electrolyte itself, reduces hydrolysis to greatest extent and brings production gas, leakage
The problems such as liquid.
Summary of the invention
The shortcomings that for existing water system liquid Zinc ion battery, present invention firstly provides a kind of completely new battery system-water
It is zinc ion colloid battery colloidal electrolyte and application.Traditional liquid electrolyte is replaced using colloidal electrolyte, purpose exists
In improving the comprehensive chemical property of water system Zinc ion battery and stability, promote the commercialization of water system Zinc ion battery into
Journey.Importantly, abandoning tradition inactive ceramic nano material, using the high new material of ionic conductivity, liquid is compared in preparation
The colloidal electrolyte of the higher conductivity of electrolyte.The colloid battery core is the preparation of colloidal electrolyte, by clay material and often
Rule liquid electrolyte is mixed with the colloidal electrolyte material with certain viscosity.
In addition, the present invention also provides the preparation method of above-mentioned colloidal electrolyte, raw material sources are extensive, low in cost, work
The advantages such as skill is simple, reproducible, environmental-friendly.
To achieve the goals above, technical solution is:
A kind of water system Zinc ion battery colloidal electrolyte, the colloidal electrolyte is by clay material, conventional electrolysis liquid structure
At colloidal electrolyte has certain viscosity and Tyndall phenomenon in colloidal state state is stablized.
The water system Zinc ion battery colloidal electrolyte, the clay material include: kaolin, Yi Laishi, green mud
One of stone, mountain tallow, attapulgite, vermiculite, allophane are a variety of compound.
Clay material microscopic appearance can be threadiness, it is spherical, it is rodlike；Microscopic dimensions are nanometer, micron or composite bulk phase.
Further, preferably concave convex rod and kaolin material.
The water system Zinc ion battery colloidal electrolyte, the clay material account for the 15% of colloidal electrolyte quality with
On.Further, preferably clay material accounts for the 40%~60% of colloidal electrolyte quality.
The water system Zinc ion battery colloidal electrolyte, the conventional liquid electrolyte is by soluble zinc salt and function
Metal salt mixes.
The water system Zinc ion battery colloidal electrolyte, soluble Zn salinity is 0.5 in the liquid electrolyte
~20mol/L.
Further, preferably soluble Zn salinity is 2~5mol/L.
The water system Zinc ion battery colloidal electrolyte, function metal salt concentrations are 0.01 in the liquid electrolyte
~1mol/L.
The water system Zinc ion battery colloidal electrolyte, the soluble zinc salt include: trifluoromethane sulfonic acid zinc Zn
(CF3SO3)2, zinc perchlorate, zinc sulfate, zinc nitrate, zinc chloride one or more compound, preferably trifluoromethane sulfonic acid zinc and sulphur
Sour zinc.
The water system Zinc ion battery colloidal electrolyte, function metal salt include: manganese salt, sodium salt, lithium salts, sylvite, magnesium
Salt, cobalt salt, nickel salt, mantoquita it is one or more compound, preferred function metal salt be manganese sulfate.
The water system Zinc ion battery colloidal electrolyte, the clay material are preceding by reusing after pre-treatment
Processing method includes: water process, acid activation, thermal activation, wet purification, supercritical ultrasonics technology, addition modifying agent, alkali modification method and microwave
One or more mixing in method.
The preparation method of the water system Zinc ion battery colloidal electrolyte: clay material is added in liquid electrolyte
It is dispersed with stirring, is aged to obtain the final product.
Further, preferably the statement time is 0.1h or more.Operation temperature is at 0 DEG C or more.
The application of the water system Zinc ion battery colloidal electrolyte: being added in diaphragm carrier as electrolyte and use, or
Person uses without using diaphragm separately as dielectric film, plays a dual role of that positive and negative anodes are isolated and ionization is connected.
A kind of water system Zinc ion battery colloidal electrolyte preparation method of the invention, specifically includes the following steps:
(1) soluble zinc salt, function metal salt solution are mixed in proportion and is completely dissolved in deionized water, institute is made
Need the liquid electrolyte of concentration.
(2) clay material is obtained into required clay material after pre-treatment or without pre-treatment.
(3) under conditions of 0 DEG C or more, resulting clay is taken to be gradually added into resulting liquid electrolyte in proportion, together
When keep continuous mechanical stirring, be aged (0.1h or more), the colloidal electrolyte with certain viscosity finally can be obtained.
The water system Zinc ion battery performance test methods of colloidal electrolyte material prepared by the present invention: weighing active material,
Conductive black, binder Kynoar, ground sufficiently rear addition NMP are mixed to form uniform black paste slurry and are coated in collection
Anode is made in processing on fluid, makees cathode with zinc metal sheet, and with colloidal electrolyte obtained, diaphragm etc. is assembled into button cell, test
Charging and discharging currents density used in cycle performance is 1000mA/g.
Technical solution of the present invention bring the utility model has the advantages that
Colloidal electrolyte material of the invention has unique zinc ion, proton conductive structure, is added by clay material conventional
Liquid electrolyte mixing is constituted.Colloid battery uses gel-like electrolyte, internal to exist without free fluid, electric under equal volume
Solution matter capacity is big, and thermal capacity is big, and heat dissipating ability is strong.Colloidal electrolyte activity water concentration is low, weak to the corrosiveness of pole plate, dense
Uniformly, electrolyte stratification phenomenon is not present in degree, and both the ion with liquid electrolyte and proton conductivity were provided simultaneously with solid-state electricity
The certain strength modulus of matter is solved, zinc salt and water are evenly distributed in gel network, avoid the phenomenon of leakage, while reducing ease gas
Amount, to environmental hazard very little.Clay material has very strong adsorption capacity, or even can be catalyzed certain gases such as H2、O2Generate water, glue
A large amount of H can be adsorbed in body netTen、SO4 2-And hydrone, moreover it is possible to adsorb Zn2+, this adds increased the electric conductivity of colloid to reduce simultaneously
Cathode hydrogen evolution phenomenon reduces the water loss in battery.
Clay material is other than with certain appearance structure, the richness of crystal structure or a kind of distinct layer net, layer chain structure
Alumina magnesia silicate contains a large amount of intermediary water in interlayer, and there is absorption water, the crystallization water, lattice watter, so microcosmic
There are excellent proton transfer channel in structure, while the atoms such as Mg, Al in crystal the energy such as can carry out with other ions and hand over
It changes, that is, there is excellent ion exchangeable.So zinc ion of the present invention can not only be adsorbed by surface and can enter electrolyte
In crystal structure, ion confinement is generated, zinc ion is created in the absolute uniform of electrolyte both macro and micro, ensures electric field action
The uniform deposition of lower ion and dispersion.Using a kind of novel electrolytes as innovative point in the present invention, key first consists in nanometer
The suspension stability and interface interaction of clay.If, can not in Ion deposition processes using micro nanoclay material
Uniform adsorption leads to the imperfect of electrode surface in electrode material surface, and destroys electrode material surface continuity, thus in electricity
Pole surface forms new catalytic site instead, increases to side reactions such as the decomposition liberations of hydrogen of aqueous electrolyte, leads to performance degradation, separately
The electrolyte containing micro clay material, which is easy to happen sedimentation lamination, outside causes battery performance unstable.On the other hand, though
Inert material is so compared, clay material can guarantee a certain amount of ionic flux, but there is also certain poor compared to liquid electrode liquid
Away from especially under high current density, it is seen that keep microelectrolysis liquid that there is certain realistic meaning in electrolyte.
In addition, clay material can be modified by water process, acid activation, thermal activation, wet purification, supercritical ultrasonics technology, addition
The processing methods such as agent, alkali modification method, microwave method carry out crystal structure and ion selectivity regulation, as by available after processing
The highly selective of zinc ion passes through, and other ion low selectivities are penetrated or are not through, and so apt avoids anode
The dissolution of the elements such as manganese (Mn), vanadium (V), cobalt (Co) causes to inactivate in material.
Water system zinc ion colloid battery made by prepared by the method colloidal electrolyte can make water system zinc ion electric
Pond obtains higher charging and discharging capacity, excellent cyclical stability, good high rate performance, outstanding high temperature performance.One
Determine the service life that water system Zinc ion battery is improved in degree, hence it is evident that improve circulating battery, high rate performance and shelving property
Can, some disadvantages of traditional electrolyte are avoided well.
Preparation water system Zinc ion battery colloidal electrolyte MATERIALS METHODS of the invention is simple and reliable, raw material sources extensively, at
This is cheap, reproducible, environmental-friendly, has wide industrial applications prospect.
Detailed description of the invention
Fig. 1 is following for the water system Zinc ion battery that 1 liquid electrolyte of comparative example and 2 colloidal electrolyte of comparative example assemble respectively
Ring volt-ampere curve comparison diagram (C-V) and cycle performance figure；
Fig. 2 is the water system Zinc ion battery that the assembling of colloidal electrolyte material is made in 1 concentration of embodiment, 23.07% kaolin
Cyclic voltammetry curve and cycle performance figure；
Fig. 3 is that the battery that the colloidal electrolyte material of embodiment 1 makes is forthright again under the conditions of different discharge-rates
It can figure；
Fig. 4 is the water system Zinc ion battery that 2 concentration of embodiment, 45% kaolin and concave convex rod colloidal electrolyte material assemble
Cyclic voltammetry curve and cycle performance figure；
Fig. 5 is the cyclic voltammetry curve and cycle performance that 3 concentration of embodiment is 33.33% kaolin colloid electrolytic cell
Figure；
Fig. 6 is using comparative example 1 and 2, embodiment 1, embodiment 2, and the battery of the material preparation of embodiment 3 is in the same terms
Under measure come AC impedance comparison diagram.
Specific embodiment
Following embodiment is described in further details to the content of present invention, and the protection scope of the claims in the present invention is not
It is restricted by the embodiment.
Comparative example 1
The zinc sulfate and manganese sulfate for weighing appropriate mass are dissolved in deionized water, be prepared into sulfuric acid zinc concentration be 2mol/L and
The liquid electrolyte of manganese sulfate concentration 0.1mol/L, and knob is assembled into using this electrolyte, zinc metal sheet cathode, manganese dioxide positive pole piece
Button water system liquid state batteries simultaneously measure its chemical property.
Circulating battery Voltammetric data is measured in CHI electrochemical workstation, determination condition: 0.1mV/s, test voltage
Range: 0.8V~1.8V.Battery carries out cycle performance test, battery charging and discharging range: 0.8V in LAND electrochemical test system
~1.8V, current density are that 1000mA/g carries out charge and discharge (similarly hereinafter) as shown in Figure 1.
Comparative example 2
The zinc sulfate and manganese sulfate for weighing appropriate mass are dissolved in deionized water, be prepared into sulfuric acid zinc concentration be 2mol/L and
The mixed solution of manganese sulfate concentration 0.1mol/L, then weigh zinc sulfate and sulfuric acid that the untreated kaolin of 1g is added to 10g
In the liquid electrolyte of manganese, i.e., clay material accounts for colloidal electrolyte mass concentration 9.09%, continuously stirs under the conditions of magnetic agitation
After mixing 1h, solution is ultrasonically treated 10min, then continuously stir 1h under the conditions of magnetic agitation, ageing 1h is obtained with one
Determine the colloidal electrolyte of viscosity and plasticity.
It is assembled into using water system Zinc ion battery colloidal electrolyte, zinc metal sheet and manganese dioxide positive pole piece manufactured in the present embodiment
Button cell, colloidal electrolyte volumetric usage and comparative example 1 are identical；Using identical electrochemical test method, as shown in Figure 1.
Fig. 1 a is that comparative example 1 shows that the cyclic voltammetry curve measured using liquid electrolyte production battery, Fig. 1 b are comparisons
The cyclic voltammetry curve that example 2 is measured using battery made by low quality score colloidal electrolyte.From figure it can be found that comparing liquid
For electrolyte, colloidal electrolyte can be substantially reduced the side reaction of first lap.Liquid electrolyte first circle is negative sweep during liquid electricity
There is faint reduction peak in the section voltage 1.4V~0.8V in pond, illustrates to be also possible to other than main reaction along with electrolyte liberation of hydrogen
It decomposes；And the battery of colloidal electrolyte is compared, only one main reaction peak does not occur it in the entire section 1.4V~0.8V
He exists at side reaction peak.The water system MnO of comparative example 1 and the preparation of 2 electrolyte of comparative example is indicated in Fig. 1 c2/ Zn water system zinc ion electricity
The cycle performance figure in pond, it can be found that liquid electrolyte is decayed as circulation carries out capacity, this is because secondary anti-in system
Answer it is lasting cause, the introducing of the colloidal electrolyte of low concentration can bring additional catalytic electrolysis liquid to react, and cause the glue
Body electrolyte is more worse than liquid electrolyte system performance instead, it can be seen that, clay mass concentration is too low to will lead to performance decline.
Embodiment 1
A part of untreated kaolin is taken first to be dissolved in deionized water, is continuously stirred under the conditions of magnetic agitation
Mixed solution is transferred to centrifuge tube after 3h, after washing, kaolin is placed under the conditions of 80 DEG C and is dried in vacuo 12h.
The zinc sulfate and manganese sulfate for weighing appropriate mass are dissolved in deionized water, be prepared into sulfuric acid zinc concentration be 2mol/L and
The mixed solution of manganese sulfate concentration 0.1mol/L, then weigh zinc sulfate and sulphur that the dried kaolin of 3g is added to 10g
In the liquid electrolyte of sour manganese, i.e., clay material accounts for colloidal electrolyte mass concentration 23.07%, under the conditions of magnetic agitation continuously
After stirring 1h, solution is ultrasonically treated 10min, then continuously stir 5h under the conditions of magnetic agitation, ageing 1h, which is obtained, to be had
The colloidal electrolyte of certain viscosity and plasticity.
It is assembled into using water system Zinc ion battery colloidal electrolyte, zinc metal sheet and manganese dioxide positive pole piece manufactured in the present embodiment
Button cell, colloidal electrolyte volumetric usage and comparative example 1 are identical；Its chemical property is tested using 1 same procedure of comparative example:
Fig. 2 is the cyclic voltammetry curve figure for showing to be measured using the battery of 1 colloidal electrolyte material of embodiment production and followed
Ring performance map.The first lap circulation of embodiment 1 is relatively flat in Fig. 2 a；And for comparative example 2, the 1st in embodiment 1,
2, the curve co-insides Du Genggao of 3 circles, implies that the side reaction occurred in battery is smaller, colloidal electrolyte can preferably protect battery
Smooth working, reduces the decomposition of electrolyte and the dissolution of positive active material and zinc dendrite is formed.In addition, Fig. 3 is embodiment 1
High rate performance figure of battery under the conditions of different discharge-rates of colloidal electrolyte material production, the as can be seen from the figure glue
Body electrolyte has good high rate performance, even if can still keep 150mAh/g's under the conditions of the heavy-current discharge of 3A/g
Charging and discharging capacity keeps the charging and discharging capacity of 100mAh/g, when current density weight under the conditions of the heavy-current discharge of 5A/g
After being newly restored to 200mA/g, charging and discharging capacity can reach 370mAh/g again again.
The charge and discharge system of cycle performance of battery test is identical as comparative example 1, and high rate performance test voltage section is in 0.8V
~1.8V, current density are respectively 200,500,1000,3000,5000mA/g then to return 200mA/g, and lower point of each electric current
It Ce Shi not 10 circles.
Embodiment 2
A part of untreated kaolin is taken first and concave convex rod (mass ratio 1:1) is dissolved in deionized water,
It continuously stirs 3h under the conditions of magnetic agitation mixed solution is transferred in centrifuge tube later, after washing, by kaolin and concave convex rod
12h is dried in vacuo under the conditions of being placed in 80 DEG C.
The zinc sulfate and manganese sulfate for weighing appropriate mass are dissolved in deionized water, be prepared into sulfuric acid zinc concentration be 2mol/L and
The mixed solution of manganese sulfate concentration 0.1mol/L, clay material account for colloidal electrolyte mass concentration 45%, in magnetic agitation condition
Under continuously stir 1h after, solution is ultrasonically treated 10min, then continuously stir 1h under the conditions of magnetic agitation, ageing 1h i.e. make
There must be the colloidal electrolyte of certain viscosity and plasticity.
It is assembled into using water system Zinc ion battery colloidal electrolyte, zinc metal sheet and manganese dioxide positive pole piece manufactured in the present embodiment
Button cell, colloidal electrolyte volumetric usage and comparative example 1 are identical；200 circle of circulation fills under the conditions of the charge and discharge of 1000mA/g
Specific discharge capacity may remain in 250.6mAh/g, as shown in Figure 4.
Embodiment 3
A part of untreated kaolin is taken first to be dissolved in deionized water, is continuously stirred under the conditions of magnetic agitation
Mixed solution is transferred in centrifuge tube after 3h, after washing, kaolin is placed under the conditions of 80 DEG C and is dried in vacuo 12h.
The zinc sulfate and manganese sulfate for weighing appropriate mass are dissolved in deionized water, be prepared into sulfuric acid zinc concentration be 3mol/L and
The mixed solution of manganese sulfate concentration 0.3mol/L, then weigh zinc sulfate and sulphur that the dried kaolin of 5g is added to 10g
In the mixed solution of sour manganese, i.e., clay material accounts for colloidal electrolyte mass concentration 33.33%, continuously stirs under the conditions of magnetic agitation
After mixing 1h, solution is ultrasonically treated 10min, then continuously stir 1h under the conditions of magnetic agitation, ageing 10h is obtained with one
Determine the colloidal electrolyte of viscosity and plasticity.
It is assembled into using water system Zinc ion battery colloidal electrolyte, zinc metal sheet and manganese dioxide positive pole piece manufactured in the present embodiment
Button cell, colloidal electrolyte volumetric usage and comparative example 1 are identical；200 circle of circulation fills under the conditions of the charge and discharge of 1000mA/g
Specific discharge capacity may remain in 170.5mAh/g, and specific capacity keeps relative stability, as shown in Figure 5.
Fig. 6 is using comparative example 1 and 2, embodiment 1, embodiment 2, and the battery of the material preparation of embodiment 3 is in the same terms
Under measure come AC impedance comparison diagram, measured in occasion China CHI 660e, test condition: 100KHz~10mHz, amplitude: 10mV,
It is measured under open-circuit voltage.Show the obtained AC impedance of colloidal electrolyte battery testing prepared in embodiment 2 in figure most
It is small, it can be found that the battery of colloidal electrolyte preparation will be small than the battery impedance of comparative example liquid electrolyte, illustrate colloid
Electrolyte has lesser ionic charge transfger impedance and higher ionic conductivity.
Embodiment 4
Yi Laishi after taking supercritical ultrasonics technology and washing process prepares colloidal electrolyte, so according to ratio in embodiment 2
After be applied to MnO2In/Zn water system Zinc ion battery, it is measured.Initial specific capacities are 286.8mA/g, in filling for 1000mA/g
200 circle charging and discharging capacity of circulation is positively retained at 235.4mAh/g under discharging condition, and specific capacity is high and capacity keeps relative stability.
Embodiment 5
Untreated Yi Laishi is taken, according to ratio in embodiment 2, wherein soluble manganese nitrate concentration is 5mol/L, function
Energy manganese nitrate salinity is 0.8mol/L, prepares colloidal electrolyte, is then applied to MnO2In/Zn water system Zinc ion battery, into
Row measurement.Initial specific capacities are 279.1mAh/g, and 200 circle charging and discharging capacities are recycled under the conditions of the charge and discharge of 1000mA/g can
It is maintained at 220.9mAh/g, specific capacity is higher and capacity keeps stablizing.
Claims (10)
1. a kind of water system Zinc ion battery colloidal electrolyte, it is characterised in that: the colloidal electrolyte is by clay material, routine
Electrolyte is constituted, and colloidal electrolyte is in stablize colloidal state state.
2. water system Zinc ion battery colloidal electrolyte according to claim 1, it is characterised in that: the clay material packet
Include: one of kaolin, Yi Laishi, chlorite, mountain tallow, attapulgite, vermiculite, allophane are a variety of compound, preferably recessed
Convex stick stone and kaolin material.
3. water system Zinc ion battery colloidal electrolyte according to claim 1, it is characterised in that: clay material microscopic appearance
It is rodlike including fibrous, spherical；Microscopic dimensions are nanometer, micron or composite bulk phase.
4. water system Zinc ion battery colloidal electrolyte according to claim 1, it is characterised in that: the clay material accounts for
15% or more of colloidal electrolyte quality, preferred concentration range are 40%~60%.
5. water system Zinc ion battery colloidal electrolyte according to claim 1, it is characterised in that: the conventional liquid electricity
Solution liquid is mixed by soluble zinc salt and function metal salt.
6. water system Zinc ion battery colloidal electrolyte according to claim 5, it is characterised in that: solvable in liquid electrolyte
Property zinc salt concentration be 0.5~20mol/L, preferred concentration range be 2~5mol/L, function metal salt concentrations be 0.01~
1mol/L。
7. water system Zinc ion battery colloidal electrolyte according to claim 5, it is characterised in that: the soluble zinc salt
It include: trifluoromethane sulfonic acid zinc Zn (CF3SO3)2, zinc perchlorate, zinc sulfate, zinc nitrate, zinc chloride it is one or more compound；
Function metal salt include: manganese salt, sodium salt, lithium salts, sylvite, magnesium salts, cobalt salt, nickel salt, mantoquita one or more compound, preferred sulphur
Sour manganese.
8. water system Zinc ion battery colloidal electrolyte according to claim 1, it is characterised in that: the clay material warp
It crosses pre-treatment to reuse later, pre-treating method includes: water process, acid activation, thermal activation, wet purification, supercritical ultrasonics technology, addition
One or more mixing in modifying agent, alkali modification method and microwave method.
9. the preparation method of the described in any item water system Zinc ion battery colloidal electrolytes of claim 1-8, it is characterised in that: will
Clay material is added to liquid electrolyte and is dispersed with stirring, is aged to obtain the final product.
10. the application of the described in any item water system Zinc ion battery colloidal electrolytes of claim 1-8, it is characterised in that: as
Electrolyte be added diaphragm carrier in use, or without using diaphragm separately as dielectric film use, play isolation positive and negative anodes and
The double action of ionization is connected.
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