CN110048104A - A kind of water system battery and preparation method thereof based on cyaniding frame material - Google Patents
A kind of water system battery and preparation method thereof based on cyaniding frame material Download PDFInfo
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- CN110048104A CN110048104A CN201910306147.6A CN201910306147A CN110048104A CN 110048104 A CN110048104 A CN 110048104A CN 201910306147 A CN201910306147 A CN 201910306147A CN 110048104 A CN110048104 A CN 110048104A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of water system battery and preparation method thereof based on cyaniding frame material, which includes positive electrode, negative electrode material and electrolyte；Positive electrode is selected from cyaniding frame composite material, and raw material includes cyaniding frame material and fluorochemical A；Cyaniding frame material is selected from sodium base cyaniding frame material, potassium base cyaniding frame material or ammonium cyaniding frame material, is prepared by coprecipitation or ion-exchange, and reaction temperature is 50~100 DEG C；Negative electrode material is selected from phosphoric acid titanium salt composite material, phosphoric acid titanium salt and fluorochemical B；The chemical general formula of phosphoric acid titanium salt is MTi2(PO4)3, in formula, M=Na+、K+、NH4 +One of or it is a variety of；Electrolyte, which is selected from, contains Na+、K+、NH4 +At least one of soluble-salt aqueous solution.The water system battery has high operating voltage, and high capacity and long cycle life are suitable as due to the intrinsic high security of water system battery in extensive energy-storage battery.
Description
Technical field
The present invention relates to the technical fields of novel energy storage cell, and in particular to a kind of water system electricity based on cyaniding frame material
Pond and preparation method thereof.
Background technique
With the fast development of the clean energy resourcies such as solar energy, wind energy, the demand to high-performance energy-storage battery is increasing.Separately
Outside, with the rise of smart grid, to exploitation novel energy storage cell, more stringent requirements are proposed.Currently, lithium ion battery, plumbic acid
Battery, flow battery etc. are widely used to energy storage.But as large-scale use, lithium provide lithium ion battery on electric car
The consumption in source is larger and depletion rate is very fast, it is difficult to maintain the sustainable development of energy-storage battery.Meanwhile organic based lithium-ion
Battery is also faced with safety issue；Lead-acid battery faces the problems such as pollution is big, the service life is short, low-response；Flow battery is then faced into
The disadvantages such as this height, energy density be low.Therefore, developing low-cost, the long-life, high-energy density novel energy storage cell have become pass
Key.
In recent years, sodium-ion battery and kalium ion battery due to resource it is extensive, cheap and be widely noticed.Traditional lithium
Ion battery uses cobalt acid lithium, LiFePO4, LiMn2O4, ternary material etc. as positive electrode, but the corresponding sodium of these materials
The chemical property of compound and potassium compound is undesirable, shows as that low capacity, low charging/discharging voltage, charge and discharge platform are unobvious etc. to be lacked
Point.
In contrast, certain cyaniding materials are conducive to the biggish sodium ion of volume, potassium ion due to having open frame
Or the insertion and abjection of ammonium ion, therefore capacity is higher, good rate capability, especially the material charging/discharging voltage containing manganese is higher,
It is adapted as sodium ion, potassium ion or ammonium ion cell positive material.In addition, since this kind of material generally closes in water phase
At, it is more stable in water, it is equipped with suitable negative electrode material, such as phosphoric acid titanium salt, safer water system battery can be formed.
As application publication number be 103022577 A of CN Chinese patent literature in disclose a kind of water system Na ion chargeable
Battery is made of cathode film, negative electrode film, the diaphragm to fall between and electrolyte with ionic conductivity, and cathode film is adopted
With sodium base Prussian-blue compound, negative electrode film uses titanium phosphate sodium compound NaTi2(PO4)3And the compound of carbon, electrolyte
Using the aqueous solution containing sodium ion.Carbon source in the compound of the titanium phosphate sodium compound and carbon is graphite, acetylene black, Super
P, one or more of interphase microballoon, vapour-phase pyrolysis carbon or organic cracking carbon.In the technical solution, due to generally using
Room temperature synthesis technology, the defects of crystal is relatively more, and sodium content is relatively low, causes capacity relatively low, even if using active metal such as Fe
When, capacity is also relatively low, and when using inactive metal such as Ni, Cu, capacity can be lower.
In addition, in water system battery, since water can decompose and certain materials chemistry/electrification in water under high voltages
Learn unstable, especially chemical/electrochemical is more unstable under high voltages.Therefore, suitable positive and negative pole material next is selected
Match, is the current main path for improving water system battery performance.
Summary of the invention
In view of the above technology scheme there are the problem of, the water system electricity that the invention discloses a kind of based on cyaniding frame material
Pond has many advantages, such as high capacity, high voltage, high circulation stability.
Specific technical solution is as follows:
A kind of water system battery based on cyaniding frame material, including positive electrode, negative electrode material and electrolyte；
The positive electrode is selected from cyaniding frame composite material, and raw material includes cyaniding frame material and fluorochemical A；
The cyaniding frame material is selected from sodium base cyaniding frame material, potassium base cyaniding frame material or ammonium cyaniding frame material
Material；
The cyaniding frame material is prepared by coprecipitation or ion-exchange, and reaction temperature is 50~100 DEG C；
The negative electrode material is selected from phosphoric acid titanium salt composite material, phosphoric acid titanium salt and fluorochemical B；
The chemical general formula of the phosphoric acid titanium salt is MTi2(PO4)3, in formula, M=Na+、K+、NH4 +One of or it is a variety of；
The electrolyte, which is selected from, contains Na+、K+、NH4 +At least one of soluble-salt aqueous solution.
The present invention by carrying out the cladding of fluoride respectively to cyaniding frame material and titanium phosphate salt, thus obtain it is special
Positive electrode and negative electrode material.
The preparation of the cyaniding frame material carries out under conditions of 50~100 DEG C, the cyaniding frame material knot being prepared
Brilliant complete, defect is less in crystal, and the content of sodium, potassium or ammonium is high.
The chemical general formula of the cyaniding frame material is denoted as MxMnFe(CN)6, in formula, M=Na+、K+、NH4 +One of
Or it is a variety of；It is found through experiment that using above-mentioned reaction temperature preparation cyaniding frame material in, can control 1.5≤x≤2.Further
It is preferred that the reaction temperature is 60~85 DEG C.
It is found through experiment that the special positive and negative electrode storeroom produces coupling or synergistic effect, so that the water finally prepared
It is that battery is provided with high voltage and high capacity, is especially that of obtaining excellent cyclical stability.
Test discovery by contrast is negative pole when with cyaniding frame material being directly anode with phosphoric acid titanium salt；Either, cyanogen
Change only one in frame material and phosphoric acid titanium salt and carries out the cladding of fluoride, the stable circulation of the water system battery finally prepared
Property is remarkably decreased.
The preparation process of the coprecipitation preparation cyaniding frame material, specific as follows:
A) by containing sodium, potassium or ammonium ferrocyanide and its corresponding salt and deionized water be mixed to get solution I；
B) Mn will be contained2+Soluble-salt and deionized water be mixed to get solution II；
C) the solution II low speed that step b) is obtained is added in the solution I for obtaining step a), through coprecipitation reaction and
Post-processing obtains the cyaniding frame material.
In step a):
The ferrocyanide containing sodium, potassium or ammonium be selected from sodium ferrocyanide, potassium ferrocyanide or ferrous ammonium cyanide or its
Respective hydrate；
Preferably, the concentration of the ferrocyanide containing sodium, potassium or ammonium is 0.05~0.5mol/L in the solution I.
Its described corresponding salt is selected from chloride corresponding with the ferrocyanide containing sodium, potassium or ammonium, fluoride, bromine
One of compound, nitrate, sulfate, sulphite, acetate, citrate or a variety of or its corresponding hydrate；
By taking sodium ferrocyanide as an example, corresponding salt is sodium chloride, sodium fluoride, sodium bromide, sodium nitrate, sodium sulphate, Asia
One of sodium sulphate, sodium acetate, sodium citrate are a variety of.
Preferably, in terms of cation, mole of described its corresponding salt and the ferrocyanide containing sodium, potassium or ammonium
Than being 10~100: 1.
For the dosage of raw material under the conditions of above-mentioned preferred, the cyaniding frame material crystallization content of preparation is good, sodium in product, potassium or
The content of ammonium is higher, and capacity is high.
In step b):
It is described to contain Mn2+Soluble-salt be selected from Mn2+Chloride, sulfate, nitrate, one of acetate or more
Kind or its corresponding hydrate；
Preferably, in the solution II, Mn2+Concentration be 0.05~0.5mol/L.
In step c):
The low speed, drop speed are 1~5 ml/min；
Preferably, the temperature of the coprecipitation reaction is 50~100 DEG C；Further preferably 60~85 DEG C.Co-precipitation is anti-
Answer temperature too low, the crystallization of cyaniding frame material is imperfect；Reaction temperature is excessively high, and the water evaporation as reaction media is too fast, influences
The formation of product.
Product after coprecipitation reaction also needs post-treated, including cooling, centrifuge separation, washing, drying process.
Under above-mentioned preferred process conditions, the cyaniding frame material crystallization content of preparation is good, and defect is less in crystal, sodium,
The content of potassium or ammonium is high, provides premise for the subsequent water system battery for preparing high capacity.
Except coprecipitation, ion-exchange preparation cyaniding frame material also can be used, specifically include:
It will be scattered in using a kind of salt containing M ion cyaniding frame material and containing another M ion of coprecipitation preparation
In deionized water, it is sufficiently stirred and is post-processed to obtain the cyaniding frame material.
Above-mentioned M ion, that is, sodium, potassium or ammonium ion.
Such as, it disperses the frame material of cyaniding containing sodium ion and salt containing ammonium ion in deionized water, through ion exchange
Method preparation is the cyaniding frame material containing ammonium ion.
Preferably, the temperature of the stirring is 50~100 DEG C, the time is 1~50h；Further preferably, whipping temp is
60~85 DEG C, mixing time is 20~40h.
Preferably, the concentration containing a kind of M ion cyaniding frame material is 0.01~0.1mol/L, it is described containing another
The salt of kind M ion, in terms of M, concentration is 0.1~1mol/L；Further preferably, the concentration of cyaniding frame material be 0.03~
0.07mol/L, salt concentration in terms of M is 0.2~0.4mol/L.
Preferably, the salt containing another M ion is selected from chloride, sulfate, sulphite, nitrate, phosphoric acid
One of salt, phosphoric acid hydrogen disalt, dihydric phosphate, three salt of citric acid or a variety of or its hydrate；Further preferably, described
Salt selective chlorination object, sulfate, nitrate.
The post-processing includes cooling, centrifuge separation, washs, is dry.The fluorochemical A be selected from fluorinated carbon material or
Metal fluoride.
Specifically:
The fluorinated carbon material be selected from fluorinated graphene, fluorinated nano carbon pipe, fluorinated nano carbon fiber, fluorinated fullerene,
It is fluorinated at least one of hard carbon, fluorination soft carbon；Preferably, by atomic percent, in the fluorinated carbon material, fluorine content 30
~60%.
The metal fluoride is in aluminum fluoride, magnesium fluoride, zinc fluoride, ferric flouride, nickel fluoride, cobaltous fluoride, copper fluoride
At least one.
In the positive electrode, cyaniding frame material and fluorochemical A are compound, and formation cyaniding frame material/containing fluorination
Close object A composite positive pole, by the modification of fluorochemical A, improve at higher voltages cyaniding frame material in water phase
Stability.
Preferably, with the total weight of the cyaniding frame composite material, the content of the fluorochemical A is 1~
10%；Further preferably 2~5%.
Preferably, the fluorine material is selected from fluorinated carbon material, it is found through experiment that, fluorinated carbon material can be with cyano frame material
Suction-operated occurs for material, to be conducive to be coated on cyano frame material surface；In addition, the intrinsic defect of fluorocarbons is conducive to sun
The insertion and abjection of ion do not influence the diffusion of cation.
Further preferably, the fluorinated carbon material is fluorinated graphene.It is found through experiment that fluorinated graphene is due to thin
Layer structure, is conducive to effectively coat cyaniding frame material, and intrinsic defect is conducive to cationic (sodium ion, potassium again
Ion or ammonium ion) diffusion；Meanwhile the hydrophobicity of fluorinated graphene can inhibit hydrone again and enter cyaniding frame material
In lattice, the destruction of material structure is prevented.
Commercially available fluorinated graphene includes single layer, bilayer, few layer and multilayer fluorinated graphene, and more preferably single layer is fluorinated stone
Black alkene.Single layer fluorinated graphene can coat uniformly, completely cyaniding frame material, and not influence the diffusion of cation.
In addition, it is raw material that the fluorographite of more cheap business, which also can be used, fluorinated graphene is made by oneself.
Specifically:
Uniform through ultrasonic disperse by Graphite fluoride Composite Deposition in organic solvent, fluorographite can be fully stripped, and be formed
Single layer fluorinated graphene.
Preferably, the fluorochemical B is selected from fluorinated carbon material or metal fluoride.
Specifically:
The fluorinated carbon material be selected from fluorinated graphene, fluorinated nano carbon pipe, fluorinated nano carbon fiber, fluorinated fullerene,
It is fluorinated at least one of hard carbon, fluorination soft carbon；Preferably, by atomic percent, in the fluorinated carbon material, fluorine content 30
~60%.
The metal fluoride is in aluminum fluoride, magnesium fluoride, zinc fluoride, ferric flouride, nickel fluoride, cobaltous fluoride, copper fluoride
At least one.
In the negative electrode material, MTi2(PO4)3It is compound with fluorochemical B, form MTi2(PO4)3/ fluorochemical B is multiple
Negative electrode material is closed, by the modification of fluorochemical B, improves MTi2(PO4)3Stability in water phase.
Preferably, with the total weight of the phosphoric acid titanium salt composite material, the content of the fluorochemical B is 1~
10%；Further preferably 2~5%.
Further preferably, the fluorinated carbon material is selected from fluorinated graphene, it is found through experiment that, fluorinated graphene is due to having
Laminate structure is conducive to effectively coat phosphoric acid titanium salt, and intrinsic defect is conducive to the diffusion of M ion again.
Commercially available fluorinated graphene includes single layer, bilayer, few layer and multilayer fluorinated graphene, and more preferably single layer is fluorinated stone
Black alkene.Single layer fluorinated graphene can coat uniformly, completely phosphoric acid titanium salt, and not influence the diffusion of M ion.
It is equally possible that commercially available fluorographite is raw material, is handled through ultrasonic disperse and obtain single layer fluorinated graphene.
Most preferably, the fluorochemical A and fluorochemical B are selected from fluorinated graphene.It is found through experiment that in use
The water system battery for stating the positive and negative electrode material assembling of special composition, recycles, capacity retention ratio is up to 91% by 50 times.
The electrolyte, which is selected from, contains Na+、K+、NH4 +At least one of soluble-salt aqueous solution, such as chloride, fluorination
Object, bromide, sulfate, sulphite, nitrate, acetate, perchlorate etc..
Preferably, in terms of cation, the concentration of the electrolyte is 3~10mol/L.By using high concentration electrolyte,
The stability of cyaniding frame material and water at higher voltages is improved, its decomposition is inhibited, while it is negative to stablize phosphoric acid titanium salt
Pole.
The invention also discloses the preparation methods of the water system battery based on cyaniding frame material, comprising:
(1) fluorochemical A, cyaniding frame material are mixed with organic solvent A, volatilizees to obtain the positive material through solvent
Material；
(2) fluorochemical B, phosphoric acid titanium salt are mixed with organic solvent B, volatilizees to obtain the negative electrode material through solvent；
(3) positive electrode, conductive agent and binder are mixed, makes anode pole piece；By the negative electrode material, conduction
Agent and binder mixing, make cathode pole piece；It is assembled into water system battery jointly with the electrolyte again.
In step (1):
The organic solvent A is selected from ethyl alcohol, ethylene glycol, glycerine, isopropanol, n,N dimethylformamide, N- methylpyrrole
At least one of alkanone；
In the organic solvent A, the concentration of fluorochemical A is 0.1~1 mg/ml, the concentration of cyaniding frame material
For 10~100 mg/mls.
In step (1), the volatilization of solvent refers to the volatilization of organic solvent A, and there are many means for making it volatilize, most commonly
By way of stirring.
In step (2):
The organic solvent B is selected from ethyl alcohol, ethylene glycol, glycerine, isopropanol, n,N dimethylformamide, N- methylpyrrole
At least one of alkanone；
In the organic solvent B, the concentration of fluorochemical B is 0.1~1 mg/ml, and the concentration of phosphoric acid titanium salt material is
10~100 mg/mls.
In step (2), the volatilization of solvent refers to the volatilization of organic solvent B, makes the means of its volatilization, most commonly by
The mode of stirring.
In step (3):
The conductive agent is selected from this field frequent species, such as acetylene black, carbon nanotubes, graphene.
The binder is selected from this field frequent species, such as polytetrafluoroethylene (PTFE), Kynoar, poly- butadiene-styrene rubber, seaweed
Sour sodium, sodium carboxymethylcellulose etc..
The type for preparing conductive agent used by the anode pole piece and the cathode pole piece and binder is independent choice
's.
Compared with prior art, the present invention has the advantage that
1, the present invention first to cyaniding frame material carry out fluoride cladding obtain positive electrode, then to phosphoric acid titanium salt into
The cladding of row fluoride obtains negative electrode material, which produces coupling or synergistic effect, so that finally
The water system battery of preparation is provided with high voltage and high capacity, is especially that of obtaining excellent cyclical stability, recycles by 50 times,
Capacity retention ratio is suitable as novel energy storage cell up to 90% or more.
2, the preparation method of water system battery disclosed by the invention, have simple process, at low cost, the period is short, low energy consumption and
The advantages that being suitble to industrialized production.
Detailed description of the invention
Fig. 1 is that the present invention is based on the structural schematic diagrams of the water system battery of cyaniding frame material；
Fig. 2 is the charging and discharging curve of the water system sodium-ion battery prepared with embodiment 1.
Specific embodiment
Embodiment 1
Sodium ferrocyanide and sodium chloride are dissolved in deionized water, are heated to 85 DEG C, is uniformly mixing to obtain with ferrous cyanogen
Radical ion meter concentration is the solution I of 0.05mol/L, and wherein the mole of sodium chloride is 80 times of sodium ferrocyanide；By manganese sulfate
It is dissolved in deionized water, obtains with Mn2+The solution that concentration is 0.05mol/L is counted, through being sufficiently stirred to obtain solution II；Then not
Under disconnected stirring, solution II is added in solution I (drop speed is 1 ml/min), gained precipitating is centrifuged, washs, drying
Obtain sodium base cyaniding frame material；It disperses business fluorographite (fluorine content 40%) in N-Methyl pyrrolidone, through super
It is 0.25g/L fluorinated graphene dispersion liquid that sonicated, which obtains concentration, then sodium base cyaniding frame material is added to above-mentioned dispersion
In liquid, wherein the weight ratio of sodium base cyaniding frame material and fluorinated graphene is 95: 5, through abundant magnetic agitation, then through centrifugation point
From, wash, be dried to obtain sodium base cyaniding frame composite positive pole；By business Graphite fluoride Composite Deposition in N-Methyl pyrrolidone
In, obtaining concentration through ultrasonication is 0.25g/L fluorinated graphene dispersion liquid, then titanium phosphate sodium is added to above-mentioned dispersion liquid
In, wherein the weight of titanium phosphate sodium and the weight ratio of fluorinated graphene are 95: 5, through abundant magnetic agitation, then be centrifuged,
It washs, be dried to obtain titanium phosphate sodium composite negative pole material；By sodium base cyaniding frame composite positive pole and titanium phosphate sodium Compound Negative
Pole material is mixed with conductive agent acetylene black and binder Kynoar respectively, respectively production anode and cathode pole piece, and with
The aqueous solution of the sodium perchlorate of 9mol/L is electrolyte, is assembled into water system sodium-ion battery, structural schematic diagram is shown in Fig. 1.
Fig. 2 is the charging and discharging curve of water system sodium-ion battery manufactured in the present embodiment, and current density is that 150mA/g (is directed to
For positive electrode, current density 1C, i.e., completion charge or discharge in 1 hour).From figure it is found that under this high current, charging is held
Amount is up to 145mAh/g, and average voltage is up to 1.5V, and due to using aqueous electrolyte, battery has high safety.Through
Cross 50 circulations, capacity retention ratio 91%.
Comparative example 1
The preparation process of sodium base cyaniding frame material and titanium phosphate sodium is with embodiment 1, but both fluoride-free graphene packets
It covers.
Water system sodium ion is assembled in such a way that embodiment 1 is same, at higher current density 150mA/g, charging capacity is
127mAh/g, average voltage 1.5V are recycled, capacity retention ratio 55% by 50 times.
Comparative example 2
The preparation process of sodium base cyaniding frame material and titanium phosphate sodium is with embodiment 1, and only sodium base cyaniding frame material carries out
Fluorinated graphene cladding, cladding process is with embodiment 1, and titanium phosphate sodium does not pass through fluorinated graphene cladding.
Water system sodium ion is assembled in such a way that embodiment 1 is same, which fills at current density 150mA/g
Capacitance is 135mAh/g, average voltage 1.5V, is recycled by 50 times, capacity retention ratio 75%.
Comparative example 3
The preparation process of sodium base cyaniding frame material and titanium phosphate sodium is with embodiment 1, and only titanium phosphate sodium has carried out fluorination stone
Black alkene cladding, cladding process is with embodiment 1, and sodium base cyaniding frame material does not pass through fluorinated graphene cladding.
Water system sodium ion is assembled in such a way that embodiment 1 is same, which fills at current density 150mA/g
Capacitance 133mAh/g, average voltage 1.5V are recycled, capacity retention ratio 70% by 50 times.
Embodiment 2
The preparation process of sodium base cyaniding frame material and titanium phosphate sodium has carried out the cladding of aluminum fluoride with embodiment 1, and
The cladding of nonfluorinated graphene, cladding process is the same as embodiment 1.
Water system sodium ion is assembled in such a way that embodiment 1 is same, the sodium-ion battery is at current density 150mA/g, warp
Cross 50 circulations, capacity retention ratio 80%.
Embodiment 3
Potassium ferrocyanide and potassium chloride are dissolved in deionized water, are heated to 85 DEG C, is uniformly mixing to obtain with ferrous cyanogen
Radical ion meter concentration is the solution I of 0.05mol/L, and wherein the mole of potassium chloride is 80 times of potassium ferrocyanide；By protochloride manganese
It is dissolved in deionized water, obtains with Mn2+The solution that concentration is 0.05mol/L is counted, through being sufficiently stirred to obtain solution II；Then not
Under disconnected stirring, solution II is added in solution I, gained precipitating is centrifuged, washs, being dried to obtain potassium base cyaniding frame material
Material；By business Graphite fluoride Composite Deposition in N-Methyl pyrrolidone, obtaining concentration through ultrasonication is 0.25g/L fluorographite
Alkene dispersion liquid, then potassium base cyaniding frame material is added in above-mentioned dispersion liquid, wherein potassium base cyaniding frame material and fluorination stone
The weight ratio of black alkene is 97: 3, through abundant magnetic agitation, then be centrifuged, wash, to be dried to obtain potassium base cyaniding frame compound
Positive electrode；By business Graphite fluoride Composite Deposition in N-Methyl pyrrolidone, obtaining concentration through ultrasonication is 0.25g/L fluorine
Graphite alkene dispersion liquid, then titanium phosphate potassium is added in above-mentioned dispersion liquid, the wherein weight and fluorinated graphene of titanium phosphate potassium
Weight ratio be 97: 3, through abundant magnetic agitation, then be centrifuged, wash, being dried to obtain titanium phosphate potassium composite negative pole material；
Potassium base cyaniding frame composite positive pole and titanium phosphate potassium composite negative pole material are mixed with conductive agent and binder respectively, respectively
Production anode and cathode pole piece, and using the aqueous solution of the potassium hyperchlorate of 9mol/L as electrolyte, it is assembled into water system kalium ion battery.
Water system kalium ion battery manufactured in the present embodiment, in the case where current density is 150mA/g, the charging capacity of the battery is high
Up to 130mAh/g, average voltage is up to 1.6V, and due to using aqueous electrolyte, battery has high safety.
Embodiment 4
Sodium base cyaniding frame material and ammonium chloride prepared by embodiment 1 are dissolved in deionized water, concentration is respectively
0.03mol/L and 0.3mol/L is stirred 30 hours at 60 DEG C, and products therefrom is centrifuged, washs, being dried to obtain ammonium cyanogen
Change frame material；By business Graphite fluoride Composite Deposition in N-Methyl pyrrolidone, obtaining concentration through ultrasonication is 0.25g/L
Fluorinated graphene dispersion liquid, then ammonium cyaniding frame material is added in above-mentioned dispersion liquid, wherein ammonium cyaniding frame material
Weight ratio with fluorinated graphene is 98: 2, through abundant magnetic agitation, then is centrifuged, washs, being dried to obtain ammonium cyaniding
Frame composite positive pole；By business Graphite fluoride Composite Deposition in N-Methyl pyrrolidone, obtaining concentration through ultrasonication is
0.25g/L fluorinated graphene dispersion liquid, then titanium phosphate sodium is added in above-mentioned dispersion liquid, wherein titanium phosphate sodium and fluorographite
The weight ratio of alkene is 98: 2, through abundant magnetic agitation, then is centrifuged, washs, being dried to obtain titanium phosphate sodium composite negative pole material
Material；Ammonium cyaniding frame composite positive pole and titanium phosphate sodium composite negative pole material are mixed with conductive agent and binder respectively,
Production anode and cathode pole piece respectively, and using the aqueous solution of the ammonium perchlorate of 9mol/L as electrolyte, it is assembled into water system ammonium ion
Battery.
Water system ammonium ion battery manufactured in the present embodiment, in the case where current density is 150mA/g, the charging capacity of the battery is high
Up to 116mh/g, average voltage is up to 1.6V, and due to using aqueous electrolyte, battery has high safety.
Claims (10)
1. a kind of water system battery based on cyaniding frame material, including positive electrode, negative electrode material and electrolyte, feature exist
In:
The positive electrode is selected from cyaniding frame composite material, including cyaniding frame material and fluorochemical A；
The cyaniding frame material is selected from sodium base cyaniding frame material, potassium base cyaniding frame material or ammonium cyaniding frame material；
The cyaniding frame material is prepared by coprecipitation or ion-exchange, and reaction temperature is 50~100 DEG C；
The negative electrode material is selected from phosphoric acid titanium salt composite material, including phosphoric acid titanium salt and fluorochemical B；
The chemical general formula of the phosphoric acid titanium salt is MTi2(PO4)3, in formula, M=Na+、K+、NH4 +One of or it is a variety of；
The electrolyte, which is selected from, contains Na+、K+、NH4 +At least one of soluble-salt aqueous solution.
2. the water system battery according to claim 1 based on cyaniding frame material, which is characterized in that the fluorochemical
A and the fluorochemical B are independently selected from fluorinated carbon material or metal fluoride.
3. the water system battery according to claim 1 based on cyaniding frame material, which is characterized in that with the cyaniding frame
The total weight of composite material, the content of the fluorochemical A are 1~10%.
4. the water system battery according to claim 1 based on cyaniding frame material, which is characterized in that with the phosphoric acid titanium salt
The total weight of composite material, the content of the fluorochemical B are 1~10%.
5. the water system battery according to claim 1 based on cyaniding frame material, which is characterized in that the fluorinated carbon material
In fluorinated graphene, fluorinated nano carbon pipe, fluorinated nano carbon fiber, fluorinated fullerene, fluorination hard carbon, fluorination soft carbon extremely
Few one kind；
The metal fluoride in aluminum fluoride, magnesium fluoride, zinc fluoride, ferric flouride, nickel fluoride, cobaltous fluoride, copper fluoride extremely
Few one kind.
6. the water system battery according to claim 5 based on cyaniding frame material, which is characterized in that the fluorinated carbon material
Selected from fluorinated graphene.
7. the water system battery according to claim 1 based on cyaniding frame material, which is characterized in that the electrolyte it is dense
Degree is 3~10mol/L.
8. a kind of preparation of the water system battery based on cyaniding frame material described in any claim according to claim 1~7
Method, it is characterised in that:
(1) fluorochemical A, cyaniding frame material are mixed with organic solvent A, volatilizees through solvent, obtains the positive electrode；
(2) fluorochemical B, phosphoric acid titanium salt are mixed with organic solvent B, volatilizees through solvent, obtains the negative electrode material；
(3) positive electrode, conductive agent and binder are mixed, makes anode pole piece；By the negative electrode material, conductive agent and
Binder mixing, makes cathode pole piece；It is assembled into water system battery jointly with the electrolyte again.
9. the preparation method of the water system battery according to claim 8 based on cyaniding frame material, which is characterized in that step
(1) in:
The organic solvent A is selected from ethyl alcohol, ethylene glycol, glycerine, isopropanol, n,N dimethylformamide, N-Methyl pyrrolidone
At least one of；
In the organic solvent A, the concentration of fluorochemical A is 0.1~1 mg/ml, and the concentration of cyaniding frame material is 10
~100 mg/mls.
10. the preparation method of the water system battery according to claim 8 based on cyaniding frame material, which is characterized in that step
Suddenly in (2):
The organic solvent B is selected from ethyl alcohol, ethylene glycol, glycerine, isopropanol, n,N dimethylformamide, N-Methyl pyrrolidone
At least one of；
In the organic solvent B, the concentration of fluorochemical B is 0.1~1 mg/ml, the concentration of phosphoric acid titanium salt material is 10~
100 mg/mls.
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