CN107697897B - Polynary layered oxide of zinc-nickel secondary batteries negative electrode material zinc titanium and preparation method thereof and the battery for using the negative electrode material - Google Patents
Polynary layered oxide of zinc-nickel secondary batteries negative electrode material zinc titanium and preparation method thereof and the battery for using the negative electrode material Download PDFInfo
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- H01M10/24—Alkaline accumulators
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Abstract
The invention discloses polynary layered oxide of a kind of zinc-nickel secondary batteries negative electrode material zinc titanium and preparation method thereof and using the battery of the negative electrode material, belong to alkaline secondary cell negative electrode field of material technology.Technical solution of the present invention main points are as follows: zinc-nickel secondary batteries negative electrode material, including the polynary layered oxide of zinc titanium, the polynary layered oxide of zinc titanium is by the polynary layered hydroxide [Zn of presoma zinc titaniumxTiyMz(OH)2]·[(Aa‑)n·mH2O] it is obtained under inert gas protection in 300-800 DEG C of high-temperature calcination.The invention further particularly discloses the preparation method of the zinc-nickel secondary batteries negative electrode material and use the zinc-nickel secondary batteries of the negative electrode material.The present invention can reduce the deformation of zinc electrode using the novel zinc-nickel secondary batteries negative electrode material, inhibits the growth of zinc dendrite and improve stability of the zinc load in lye, and the service life cycle of zinc-nickel secondary batteries is greatly improved.
Description
Technical field
The invention belongs to alkaline secondary cell negative electrode field of material technology, and in particular to a kind of zinc-nickel secondary batteries cathode material
Material and preparation method thereof and the battery for using the negative electrode material.
Background technique
Zinc-nickel cell has that specific energy is big, specific power is high and cost performance is high etc. solely as a kind of novel alkaline secondary cell
Special advantage is widely used in various energy storage devices by people.Zinc-nickel secondary batteries market is currently in fast development, however,
The type battery has a problem that be exactly that cycle life relative to other secondary cells wants poor, and it is secondary that this is mainly due to zinc-nickels
The zinc load that battery uses the problems such as there are deformation and dendrite, its cycle performance is caused to decline.For this problem, research work
Person has done a lot of research work to the improvement of zinc load, wherein using various additives, including cathode additive agent, electrolyte add
The technological means such as agent alleviate these problems.For example electrolyte prescription is improved, other than being saturated zinc oxide, is passed through
The use of some benefit-additives such as sodium fluoride, sodium phosphate etc. significantly reduces solubility of the zinc in alkaline solution, thus
Improve the performance of zinc electrode.In addition, the materials such as some novel anode materials such as calcium zincates, zinc-aluminum hydrotalcite are also by research work
Person is proposed for use as zinc negative active substance, these new materials also improve the cyclicity of zinc-nickel secondary batteries to a certain extent
Energy.
The patent of Publication No. CN103579588A discloses a kind of that the zinc-base with layer structure is ternary layered compound
Oxide applications are to the method in the zinc electrode of zinc-nickel secondary batteries, and the layered mixed oxide is mainly using containing before aluminum hydrotalcite
Body preparation, although the layered mixed oxide can preferably solve the problems, such as zinc load deformation to a certain extent,
It has a certain impact to the capacity of battery.Meanwhile in cyclic process, can there are problems that aluminium dissolves out using containing aluminum oxide.This
Outside, since the presence of aluminium element will cause the decline of material high rate performance.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of zinc-nickel secondary batteries negative electrode material that cycle performance is excellent and
Preparation method, using the novel zinc-nickel secondary batteries negative electrode material can reduce zinc electrode deformation, inhibit zinc dendrite at
Stability long and that improvement zinc load is in lye, greatly improves the service life cycle of zinc-nickel secondary batteries.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, zinc-nickel secondary batteries negative electrode material, feature
It is to include the polynary layered oxide of zinc titanium, the polynary layered oxide of zinc titanium is by the polynary layered hydroxide of presoma zinc titanium
[ZnxTiyMz(OH)2]·[(Aa-)n·mH2O] it is obtained under inert gas protection in 300-800 DEG C of high-temperature calcination, wherein Aa-For
CO3 2-、BO2 -、PO4 3-、SO4 2-、OH-、Cl-、F-、S2-、MoO4 2-、WO4 2-, citrate, borate, benzoate anion, dodecyl
One of benzene sulfonic acid root, dodecyl sulphate root or dodecyl sodium sulfonate root are a variety of, M Cu, Bi, Ce, Sn or In, and 0.9
>=x >=0.5,0.5 > y > 0,0.5 > z > 0, x+y+z=1, m > 0, n > 0.
The preparation method of zinc-nickel secondary batteries negative electrode material of the present invention, it is characterised in that the polynary stratiform of zinc titanium
The specific synthesis step of oxide are as follows:
(1) in draught cupboard, titanium tetrachloride solution is dissolved in deionized water, soluble zinc salt is added, by titanium tetrachloride
Molar ratio control with soluble zinc salt is 1≤Zn/Ti≤9, adds soluble copper salt, soluble bismuth salt, solubility
One of cerium salt, soluble pink salt or soluble indium salts and urea, it is 0.5-7mol/L's that molar concentration is configured to after stirring
Composite compaction technique；
(2) by composite compaction technique move into hydrothermal reaction kettle in 100-200 DEG C hydro-thermal process 4-72 hours, then carried out
Filter obtains intermediate product white powder；
(3) by white powder be transferred to by alkaline hydrated oxide, phosphate, tungstates, molybdate, chlorate, fluoride salt,
Carbonate, metaborate, borate, citrate, benzoate, dodecyl benzene sulfonate, lauryl sulfate or ten
One of dialkyl group sulfonate or the total mol concentration of a variety of preparations are in the solution of 0.1-7mol/L, in inert nitrogen gas
Or in 25-200 DEG C of processing 1-24h under argon atmosphere or air atmosphere, using filter, washs, is dried to obtain intermediate products；
(4) gained intermediate products are small in 300-800 DEG C of high-temperature calcination 1-20 under inert nitrogen gas or argon atmosphere
When obtain the polynary layered oxide of target product zinc titanium.
Further preferably, the soluble zinc salt is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride；The soluble copper
Salt is copper nitrate, copper sulphate, copper acetate or copper chloride；The soluble bismuth salt is bismuth nitrate, bismuth sulfate, bismuth acetate or chlorination
Bismuth；The solubility cerium salt is cerous nitrate, cerous sulfate, cerous acetate or cerium chloride；The solubility pink salt is nitric acid tin, sulfuric acid
Tin, tin acetate or stannic chloride；The solubility indium salts are indium nitrate, indium sulfate, indium acetate or inidum chloride.
Further preferably, the alkaline hydrated oxide is sodium hydroxide, potassium hydroxide or lithium hydroxide.
Further preferably, the phosphate is one of potassium phosphate, dibastic sodium phosphate or sodium phosphate or a variety of；The wolframic acid
Salt is one of potassium tungstate, sodium tungstate or tungstate lithium or a variety of；The molybdate is that potassium molybdate or sodium molybdate are one or more；
The chlorate is one or more in potassium chloride or sodium chloride；The fluoride salt is a kind of or more in potassium fluoride or sodium fluoride
Kind；The sulphurizing salt is one or more in potassium sulfide or vulcanized sodium；The carbonate be it is a kind of in potassium carbonate or sodium carbonate or
It is a variety of；The metaborate is one of potassium metaborate, kodalk or lithium metaborate or a variety of；The borate is inclined boron
One of sour potassium, kodalk or lithium metaborate are a variety of；The citrate is one in potassium citrate and sodium citrate
Kind or two kinds；The benzoate is one or both of Potassium Benzoate and sodium benzoate；The dodecyl benzene sulfonate
For neopelex；The lauryl sulfate is lauryl sodium sulfate；The dodecane sulfonate is ten
Dialkyl sulfonates.
Zinc-nickel secondary batteries negative plate of the present invention, it is characterised in that: the zinc-nickel secondary batteries negative plate be by
What above-mentioned zinc-nickel secondary batteries negative electrode material was prepared, the zinc-nickel secondary batteries negative electrode material be used as main active substances or/
With zinc oxide cathode additive agent.
Further preferably, the polynary layered oxide of zinc titanium is used as main active substances, and the active material of electrode is by 60-
The polynary layered oxide of zinc titanium, the additive of 5-30 parts by weight, the conductive agent of 5-10 parts by weight and the 1-5 weight of 90 parts by weight
The binder composition of part, wherein additive is bismuth sulfide, bismuth oxide, cuprous sulfide, indium oxide, zinc oxide, ceria, vulcanization
Stannous or stannous oxide it is one or more, conductive agent is electrically conductive graphite, conductive carbon black, sub- titanium oxide, indium powder, aluminium powder, glass putty
Or one of copper powder or a variety of, binder are sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene (PTFE), hydroxypropyl methyl fibre
Tie up the one or more of element, Sodium Polyacrylate, polyethylene, Pluronic F-127 or butadiene-styrene rubber.
Further preferably, the polynary layered oxide of zinc titanium is used as zinc oxide cathode additive agent, the active material of electrode
By the zinc oxide of 60-90 parts by weight, the polynary layered oxide of zinc titanium, the additive of 10-20 parts by weight, 5- of 1-30 parts by weight
The conductive agents of 10 parts by weight and the binder of 1-5 parts by weight composition, wherein additive be bismuth sulfide, bismuth oxide, cuprous sulfide,
Indium oxide, zinc oxide, ceria, stannous sulfide or stannous oxide it is one or more, conductive agent is electrically conductive graphite, conductive carbon
One of black, sub- titanium oxide, indium powder, aluminium powder, glass putty or copper powder are a variety of, and binder is sodium carboxymethylcellulose, polyethylene
Alcohol, polytetrafluoroethylene (PTFE), hydroxypropyl methyl cellulose, Sodium Polyacrylate, polyethylene, Pluronic F-127 or butadiene-styrene rubber one kind or
It is a variety of.
Zinc-nickel secondary batteries of the present invention, including battery case and it is sealed in the intracorporal polar plate group of battery case and electrolysis
Liquid, wherein polar plate group includes positive plate, negative plate and diaphragm, it is characterised in that: the negative plate is secondary using above-mentioned zinc-nickel
Cell negative plate.
Compared with the prior art, the invention has the following beneficial effects: the polynary layered oxide of zinc titanium has excellent structure
Stability；A large amount of In-situ reactions beneficial to titanium elements and other metallic elements are significantly improved beneficial to the doping vario-property of anion
The distribution of Zn-ef ficiency in the electrodes, it is suppressed that the formation of zinc dendrite.In addition, importantly, the overpotential of hydrogen evolution of electrode obtains
To improvement, it is possible to reduce the generation of evolving hydrogen reaction, corrosion mitigating effect is obvious, and the structural stability of zinc electrode and hypovolemic is greatly improved
Energy.The electric conductivity of the material is improved simultaneously, to reduce activation polarization of the electrode in charge and discharge process, improves electricity
The high rate performance and cycle performance in pond.The 0.2C gram volume of the new material can achieve 560mAh/g, and 5C capacity can achieve
430mAh/g.There is specific energy height, specific power using zinc-nickel secondary batteries prepared by the novel zinc-nickel secondary batteries negative electrode material
Height and the advantages of having extended cycle life.
Detailed description of the invention
Fig. 1 is the SEM of the polynary layered oxide of zinc titanium (Zn/Ti/Cu=4/0.8/0.2) negative electrode material of embodiment preparation
Figure.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
The preparation of zinc titanium copper layered oxide (Zn/Ti/Cu=4/1/1) negative electrode material:
In draught cupboard, titanium tetrachloride solution is dissolved in a certain amount of deionized water, zinc chloride and copper chloride is added, it will
The control of the molar ratio of titanium tetrachloride and zinc salt is Zn/Ti/Cu=4/1/1, adds a certain amount of urea, prepares after stirring
The composite compaction technique for being 3mol/L at molar concentration；Composite compaction technique is moved into hydrothermal reaction kettle in 170 DEG C of hydro-thermal process 25
Hour, it is then filtered, obtains intermediate product white powder；It is 1mol/L sodium phosphate that white powder, which is transferred to molar concentration,
In solution, in 70 DEG C of processing 5h under inert nitrogen gas, using filter, washs, is dried to obtain intermediate products, among gained
Product obtains target product in high-temperature calcination 5 hours in 500 DEG C under inert nitrogen gas.
The production of negative plate:
It is 2.5% by negative electrode active material 80g obtained, zinc powder 5g, conductive carbon black 5g, bismuth sulfide 5g, mass concentration
The PTFE aqueous solution 0.3g that the poly-vinyl alcohol solution 0.5g and mass concentration that CMC solution 1g, mass concentration are 4% are 60% is mixed
Uniformly negative electrode slurry is made in conjunction, is applied on copper strips two sides by coating-spreading mould, by drying, roll-in, cuts negative plate is made.
Embodiment 2
The preparation of zinc titanium copper layered oxide (Zn/Ti/In=3/1/1) negative electrode material:
In draught cupboard, titanium tetrachloride solution is dissolved in a certain amount of deionized water, zinc chloride and inidum chloride is added, it will
The control of the molar ratio of titanium tetrachloride and zinc salt is Zn/Ti/Cu=3/1/1, adds a certain amount of urea, prepares after stirring
The composite compaction technique for being 1mol/L at molar concentration；Composite compaction technique is moved into hydrothermal reaction kettle in 180 DEG C of hydro-thermal process 15
Hour, it is then filtered, obtains intermediate product white powder；White powder, which is transferred to the molar concentration that pH value is 14, is
The sodium tungstate alkaline solution of 2.0mol/L, in 100 DEG C of processing 10h under inert nitrogen gas, using filter, washing, dry
To intermediate products, gained intermediate products are obtained into target product in high-temperature calcination 2 hours in 600 DEG C under inert nitrogen gas.
The production of negative plate:
By negative electrode active material 81g obtained, zinc powder 8g, sub- titanium oxide 5g, zinc oxide 5g, bismuth oxide 5g, mass concentration
For 2.5% CMC solution 1g, mass concentration be 25% SBR solution 0.3g and mass concentration be 60% PTFE aqueous solution
0.3g is uniformly mixed and negative electrode slurry is made, and is applied on copper strips two sides by coating-spreading mould, by drying, roll-in, cuts and is made
Negative plate.
Embodiment 3
The preparation of zinc titanium tin layered oxide (Zn/Ti/Sn=3/1/0.5) negative electrode material:
In draught cupboard, titanium tetrachloride solution is dissolved in a certain amount of deionized water, zinc sulfate and acid chlorization is added
The molar ratio control of Zn/Ti/Sn is 3/1/0.5, adds a certain amount of urea, be configured to rub after stirring by solution of tin
The composite compaction technique that your concentration is 2mol/L；By composite compaction technique move into hydrothermal reaction kettle in 150 DEG C hydro-thermal process 36 hours,
Then it is filtered, obtains intermediate product white powder；White powder is transferred to the dodecane that molar concentration is 0.5mol/L
In base benzene sulfonic acid sodium salt solution, in 140 DEG C of processing 6h under inert nitrogen gas, using filter, washs, is dried to obtain intermediate production
Gained intermediate products are obtained target product in high-temperature calcination 10 hours in 450 DEG C under inert nitrogen gas by product.
The production of negative plate:
It is by negative electrode active material 82g obtained, zinc powder 8g, electrically conductive graphite 5g, indium powder 1g, cerium oxide 5g, mass concentration
The PTFE aqueous solution 0.3g that the SBR solution 0.4g and mass concentration that 2.5% CMC solution 1g, mass concentration are 25% are 60%
It is uniformly mixed and negative electrode slurry is made, be applied on copper strips two sides by coating-spreading mould, by drying, roll-in, cut cathode is made
Plate.
Embodiment 4
The preparation of zinc titanium cerium layered oxide (Zn/Ti/Ce=3/1/1) negative electrode material:
In draught cupboard, titanium tetrachloride solution is dissolved in a certain amount of deionized water, zinc chloride and cerium chloride is added, it will
The molar ratio control of Zn/Ti/Ce is 3/1/1, adds a certain amount of urea, being configured to molar concentration after stirring is
The composite compaction technique of 1mol/L；By composite compaction technique move into hydrothermal reaction kettle in 120 DEG C hydro-thermal process 48 hours, then carry out
Filtering obtains intermediate product white powder；It is the sodium fluoride of 3mol/L, sodium phosphate and partially that white powder, which is transferred to molar concentration,
In the solution of Boratex (sodium fluoride: trisodium citrate: the molar ratio of sodium phosphate be 0.2:2:1), under inert nitrogen gas in
135 DEG C of processing 20h using filter, are washed, are dried to obtain intermediate products, by gained intermediate products 550 under inert nitrogen gas
DEG C obtain target product within high-temperature calcination 6 hours.
The production of negative plate:
By negative electrode active material 84g obtained, zinc powder 8g, superconduction carbon black 5g, copper powder 3g, stannous oxide 5g, indium oxide
The poly-vinyl alcohol solution 0.5g and mass concentration that CMC solution 1g that 3g, mass concentration are 2.5%, mass concentration are 4% be
60% PTFE aqueous solution 0.3g is uniformly mixed and negative electrode slurry is made, and is applied on copper strips two sides by coating-spreading mould, through overdrying
Dry, roll-in cuts negative plate is made.
Embodiment 5
The preparation of zinc titanium bismuth layered oxide (Zn/Ti/Bi=3/1/0.5) negative electrode material:
In draught cupboard, titanium tetrachloride solution is dissolved in a certain amount of deionized water, zinc chloride and nitric acid bismuthic acid is added
Property solution, be 3/1/0.5 by the control of the molar ratio of Zn/Ti/Bi, add a certain amount of urea, be configured to rub after stirring
The composite compaction technique that your concentration is 6mol/L；By composite compaction technique move into hydrothermal reaction kettle in 140 DEG C hydro-thermal process 48 hours,
Then it is filtered, obtains intermediate product white powder；It is 4mol/L that white powder, which is transferred to the molar concentration that pH value is 14,
Trisodium citrate alkaline solution in, under inert nitrogen gas for 24 hours in 60 DEG C of processing, using filter, wash, be dried to obtain
Gained intermediate products are obtained target product in high-temperature calcination 5 hours in 650 DEG C under inert nitrogen gas by intermediate products.
The production of negative plate:
Negative electrode active material 84g obtained, zinc powder 8g, superconduction carbon black 5g, stannous sulfide 5g, indium oxide 3g, quality is dense
Spend the HPMC solution 1g for 2.5%, the poly-vinyl alcohol solution 0.5g that mass concentration is 4% and the PTFE that mass concentration is 60%
Aqueous solution 0.3g is uniformly mixed and negative electrode slurry is made, and is applied on copper strips two sides by coating-spreading mould, by drying, roll-in, sanction
Cut into negative plate.
Embodiment 6
It is by weight as additive and commercial oxidation zinc by zinc titanium tin layered oxide (Zn/Ti/Sn=3/1/0.5)
Make active material after 1:4 mixing.
The production of negative plate:
By negative electrode active material 80g obtained, superconduction carbon black 8g, copper powder 4g, bismuth sulfide 6g, indium oxide 2g, mass concentration
For 2.5% CMC solution 1g, mass concentration be 4% poly-vinyl alcohol solution 0.5g and mass concentration be 60% PTFE it is water-soluble
Liquid 0.3g is uniformly mixed and negative electrode slurry is made, and is applied on copper strips two sides by coating-spreading mould, by drying, roll-in, cuts system
At negative plate.
Comparative example 1
Active material is done using commercial oxidation zinc.
The production of negative plate: by commercial oxidation Zinc material 84g, zinc powder 8g, superconduction carbon black 5g, bismuth oxide 5g, indium oxide
The poly-vinyl alcohol solution 0.5g and mass concentration that HPMC solution 1g that 2g, mass concentration are 2.5%, mass concentration are 4% be
60% PTFE aqueous solution 0.3g is uniformly mixed and negative electrode slurry is made, and is applied on copper strips two sides by coating-spreading mould, through overdrying
Dry, roll-in cuts negative plate is made.
Battery assembly:
It will be pressed from both sides between the cathode prepared and the positive plate of sintering across zinc-nickel cell in above-described embodiment 1-6 and comparative example 1
Dedicated diaphragm is fitted into special simulated battery shell, and the KOH and mass concentration that the mass concentration of injection ZnO saturation is 30% are 2%
LiOH electrolyte, be assembled into the zinc-nickel secondary batteries of semitight.
Battery performance test:
By the battery made of specific embodiment 1-6 and comparative example 1 after 0.2C is activated, 0.2C charging 6h, Zhi Hou electricity
30min is shelved in pond, is then discharged to voltage respectively with 0.2C and 5C as 1.4V and 1.2V, is measured the volumetric properties of negative electrode material.
Cycle performance of battery test: battery made from negative electrode active material prepared by embodiment 1-6 is respectively under 25 DEG C of environment temperatures
1C charge-discharge test is carried out, capacity attenuation terminates test with the 80% of peak capacity.Battery electrical property test result is listed in table 1.
1 battery charging/discharging performance testing of table
It can be seen that from the above test result using negative electrode material prepared by the present invention gram volume with higher, excellent
Cyclical stability and higher energy density per unit volume, be able to satisfy the requirement of commercial cells, especially high-capacity battery.These property
Can improvements be mainly due to the optimization of synthetic method, beneficial zwitterion to the modification of negative electrode material structural lattice, with
And the optimization of electrode formulation, the presence of especially a large amount of beneficial metallic elements greatly reduce the deformation of cathode, hence it is evident that inhibit its analysis
Hydrogen reaction, so as to improve the overall performance of cathode.
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (9)
1. zinc-nickel secondary batteries negative electrode material, it is characterised in that including the polynary layered oxide of zinc titanium, the polynary stratiform oxygen of the zinc titanium
Compound is by the polynary layered hydroxide [Zn of presoma zinc titaniumxTiyMz(OH)2]·[(Aa-)n·mH2O] under inert gas protection
It is obtained in 300-800 DEG C of high-temperature calcination, wherein Aa-For CO3 2-、BO2 -、PO4 3-、SO4 2-、OH-、Cl-、F-、S2-、MoO4 2-、WO4 2-、
In citrate, borate, benzoate anion, dodecyl benzene sulfonic acid root, dodecyl sulphate root or dodecyl sodium sulfonate root
It is one or more, M Cu, Bi, Ce, Sn or In, 0.9 >=x >=0.5,0.5 > y > 0,0.5 > z > 0, x+y+z=1, m > 0, n >
0。
2. a kind of preparation method of zinc-nickel secondary batteries negative electrode material described in claim 1, it is characterised in that the zinc titanium is more
The specific synthesis step of first layered oxide are as follows:
(1) in draught cupboard, titanium tetrachloride solution is dissolved in deionized water, be added soluble zinc salt, by titanium tetrachloride with can
The molar ratio control of soluble zinc salt is 1≤Zn/Ti≤9, add soluble copper salt, soluble bismuth salt, soluble cerium salt,
One of soluble pink salt or soluble indium salts and urea are configured to the complex salt that molar concentration is 0.5-7mol/L after stirring
Solution；
(2) by composite compaction technique move into hydrothermal reaction kettle in 100-200 DEG C hydro-thermal process 4-72 hours, be then filtered,
Obtain intermediate product white powder；
(3) white powder is transferred to by alkaline hydrated oxide, phosphate, tungstates, molybdate, chlorate, fluoride salt, carbonic acid
Salt, metaborate, borate, citrate, benzoate, dodecyl benzene sulfonate, lauryl sulfate or dodecane
One of base sulfonate or the total mol concentration of a variety of preparations are in the solution of 0.1-7mol/L, in inert nitrogen gas or argon
In 25-200 DEG C of processing 1-24h under gas atmosphere or air atmosphere, using filter, washs, is dried to obtain intermediate products；
(4) gained intermediate products are obtained under inert nitrogen gas or argon atmosphere in 300-800 DEG C for high-temperature calcination 1-20 hours
To the polynary layered oxide of target product zinc titanium.
3. the preparation method of zinc-nickel secondary batteries negative electrode material according to claim 2, it is characterised in that: the solubility
Zinc salt is zinc nitrate, zinc sulfate, zinc acetate or zinc chloride；The soluble copper salt is copper nitrate, copper sulphate, copper acetate or chlorination
Copper；The soluble bismuth salt is bismuth nitrate, bismuth sulfate, bismuth acetate or bismuth chloride；The solubility cerium salt is cerous nitrate, sulfuric acid
Cerium, cerous acetate or cerium chloride；The solubility pink salt is nitric acid tin, STANNOUS SULPHATE CRYSTALLINE, tin acetate or stannic chloride；The solubility indium salts
For indium nitrate, indium sulfate, indium acetate or inidum chloride.
4. the preparation method of zinc-nickel secondary batteries negative electrode material according to claim 2, it is characterised in that: the alkaline hydrogen
Oxide is sodium hydroxide, potassium hydroxide or lithium hydroxide.
5. the preparation method of zinc-nickel secondary batteries negative electrode material according to claim 2, it is characterised in that: the phosphate
For one of potassium phosphate, dibastic sodium phosphate or sodium phosphate or a variety of；The tungstates is in potassium tungstate, sodium tungstate or tungstate lithium
It is one or more；The molybdate is that potassium molybdate or sodium molybdate are one or more；The chlorate is in potassium chloride or sodium chloride
It is one or more；The fluoride salt is one or more in potassium fluoride or sodium fluoride；The carbonate is potassium carbonate or sodium carbonate
In it is one or more；The metaborate is one of potassium metaborate, kodalk or lithium metaborate or a variety of；The boric acid
Salt is one of potassium borate, Boratex or lithium borate or a variety of；The citrate is in potassium citrate and sodium citrate
It is one or two kinds of；The benzoate is one or both of Potassium Benzoate and sodium benzoate；The dodecyl benzene sulfonic acid
Salt is neopelex；The lauryl sulfate is lauryl sodium sulfate；The dodecane sulfonate is
Dodecyl sodium sulfate.
6. a kind of zinc-nickel secondary batteries negative plate, it is characterised in that: the zinc-nickel secondary batteries negative plate is by claim 1 institute
What the zinc-nickel secondary batteries negative electrode material stated was prepared, the zinc-nickel secondary batteries negative electrode material be used as main active substances or/
With zinc oxide cathode additive agent.
7. zinc-nickel secondary batteries negative plate according to claim 6, it is characterised in that: the polynary layered oxide of zinc titanium
As main active substances, the active material of electrode is by the polynary layered oxides of zinc titanium of 60-90 parts by weight, 5-30 parts by weight
The binder of additive, the conductive agent of 5-10 parts by weight and 1-5 parts by weight forms, and wherein additive is bismuth sulfide, bismuth oxide, sulphur
Change the one or more of cuprous, indium oxide, zinc oxide, ceria, stannous sulfide or stannous oxide, conductive agent is conductive stone
One of ink, conductive carbon black, sub- titanium oxide, indium powder, aluminium powder, glass putty or copper powder are a variety of, and binder is carboxymethyl cellulose
Sodium, polyvinyl alcohol, polytetrafluoroethylene (PTFE), hydroxypropyl methyl cellulose, Sodium Polyacrylate, polyethylene, Pluronic F-127 or butylbenzene rubber
Glue it is one or more.
8. zinc-nickel secondary batteries negative plate according to claim 6, it is characterised in that: the polynary layered oxide of zinc titanium
As zinc oxide cathode additive agent, the active material of electrode is by the zinc oxide of 60-90 parts by weight, the zinc titanium layer shape of 1-30 parts by weight
Multivariant oxide, the additive of 10-20 parts by weight, the conductive agent of 5-10 parts by weight and 1-5 parts by weight binder composition, wherein
Additive is the one of bismuth sulfide, bismuth oxide, cuprous sulfide, indium oxide, zinc oxide, ceria, stannous sulfide or stannous oxide
Kind is a variety of, and conductive agent is one of electrically conductive graphite, conductive carbon black, sub- titanium oxide, indium powder, aluminium powder, glass putty or copper powder or more
Kind, binder is sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene (PTFE), hydroxypropyl methyl cellulose, Sodium Polyacrylate, gathers
Ethylene, Pluronic F-127 or butadiene-styrene rubber it is one or more.
9. a kind of zinc-nickel secondary batteries, including battery case and it is sealed in the intracorporal polar plate group of battery case and electrolyte, wherein pole
Board group includes positive plate, negative plate and diaphragm, it is characterised in that: the negative plate is using any one of claim 6-8 institute
The zinc-nickel secondary batteries negative plate stated.
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| CN111244399B (en) * | 2018-11-28 | 2021-11-26 | 中南大学 | Metal oxide modified zinc oxide tube composite negative electrode material for zinc secondary battery and preparation method thereof |
| CN110931771A (en) * | 2019-12-10 | 2020-03-27 | 河南创力新能源科技股份有限公司 | Preparation method of high-activity negative electrode material of alkaline secondary battery |
| CN111009653B (en) * | 2019-12-10 | 2022-12-09 | 河南创力新能源科技股份有限公司 | Preparation method of zinc cathode material of zinc-nickel secondary battery |
| CN114551873A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Bismuth trioxide modified indium-doped zinc oxide material and preparation and application thereof |
| CN116425189B (en) * | 2022-08-29 | 2024-05-10 | 河南师范大学 | ZnO@ZnS@C composite negative electrode material for zinc-nickel secondary battery and preparation method and application thereof |
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