CN106450508A - Bismuth vanadium/nickel hydroxide secondary alkaline battery and preparation method thereof - Google Patents
Bismuth vanadium/nickel hydroxide secondary alkaline battery and preparation method thereof Download PDFInfo
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- CN106450508A CN106450508A CN201611085421.4A CN201611085421A CN106450508A CN 106450508 A CN106450508 A CN 106450508A CN 201611085421 A CN201611085421 A CN 201611085421A CN 106450508 A CN106450508 A CN 106450508A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a bismuth vanadium/nickel hydroxide secondary alkaline battery and a preparation method thereof. BiVO4 (bismuth vanadium) materials are used as a negative electrode of the battery, nickel hydroxide materials are used as a positive electrode of the battery, alkaline solution is electrolyte solution, and a voltage window of the battery is 0.5-1.5V. The bismuth vanadium materials are prepared in an organic solvent system by a chemical precipitation method, a solvothermal method and a chemical precipitation and solvothermal combined method, the specific surface area of the prepared materials is 10-500m<2>/g, the specific capacity of the prepared battery is 201.9mAh/g when current density is 1A/g, and the retention rate of the electric capacity of the battery after cycle for 500 times reaches up to 81%. The prepared battery is environmentally friendly, high in coulombic efficiency and long in cycle life, and is an alkaline secondary chemical power source with a wide application prospect.
Description
Technical field
The invention belongs to electrochemical energy storage field, more particularly to a kind of pucherite (BiVO4The secondary alkaline electro of)/nickel hydroxide
Pond and preparation method thereof.
Background technology
Since entering 21 century, environmental resource problem is highlighted, and people need the energy-saving and emission-reduction that are not only that does, and reduce pollution,
Exploitation cleaning green energy resource is also needed to mitigating the pressure of resource and environment, therefore the research of efficient energy storage device is also just very
Urgently.In recent years, portable electric appts are developed rapidly so that novel secondary battery should meet small volume, light weight, capacity
High, life-span length demand.Propose new cells concepts, develop new electrode material, study new battery system be battery technology not
Disconnected progressive power producer, the even more focus of energy storage area research.
It is all tradition the nickel/cadmium cell of positive pole, nickel iron battery, nickel/hydrogen battery, nickel zinc battery etc. to be done using nickel hydroxide
Secondary alkaline batteries, but also all there are some problems, such as, durable, but main raw material(s) component cadmium stablized by nickel-cadmium cell
Toxicity is big, high cost, pollutes environment；Nickel iron cell self-discharge rate height, poor performance at low temperatures；The Ni-MH battery charging interval is than NI-G electricity
Pond is long, and self discharge increases with temperature and increases；The zinc electrode of nickel-zinc cell easily forms dendrite causes life-span variation etc..In consideration of it,
People need to explore new secondary alkaline batteries.
Bismuthino toxicity of compound is little, low cost, all grinds in catalyst, gas sensor, electrode material, optical material
Study carefully application.Bismuth hydrate., bismuth oxide, bismuth ferrite, bismuth molybdate, bismuth oxide etc., or they and Graphene, nano titania
The composite of pipe, polyaniline, manganese dioxide etc. has been studied as electrode material.
[the ECS Transactions 28 (2010) such as Xia:125] bismuth oxide nanometer sheet is prepared for by chemical precipitation method
For electrochemical capacitor, specific capacity is 996F g-1, only decayed 4.2% after 1000 charge and discharge cycles.Nie etc.
[Electrochimica Acta 154(2015):30] bismuth sulfide/graphene composite material is prepared by simple hydro-thermal reaction,
And have studied capacitive property.[the Journal of The Electrochemical Society 159 (2012) such as Liu:586]
The molybdic acid bismuth nano-wire of high-specific surface area is prepared for by way of electrochemical deposition is with reference to heat treatment and have studied which super
Application in capacitor.[the Journal of Power Sources 195 (2010) such as Kang:2023] BiOF cladding have studied
Li [Ni0.5Mn1.5]O4Application in chargeable lithium cell.
Patent of invention [application publication number CN103224251A] discloses a kind of " microwave synthesis monoclinic system olive shape vanadic acid
Bismuth BiVO4Preparation method ", the invention is under reflux conditions in the ethylene glycol solution of microwave heating bismuth nitrate and ammonium metavanadate,
Olive-type pucherite material is prepared.Patent of invention [Authorization Notice No. CN102557133B] discloses that " one kind adopts microwave
Hydro-thermal method prepares fish spicule shape and firewood shape BiVO4The method of powder body ", the invention is by the salpeter solution of bismuth nitrate and ammonium metavanadate
Sodium hydroxide solution is uniformly mixed so as to obtain predecessor, with NaOH adjust pH value, then carry out microwave hydrothermal reaction prepare fish spicule shape and wood
The bismuth vanadate powder that the monoclinic phase of bavin shape is blended with Tetragonal.Patent of invention [application publication number CN103145185A] is disclosed
" a kind of processing technology of ultra-fine pucherite ", aqueous bismuth nitrate solution is mixed by the invention with the aqueous solution atomization of ammonium metavanadate, with
Ammonia adjusts pH value, and abundant precipitation under room temperature obtains ultra-fine pucherite.
Yet there are no the relevant report of the secondary alkaline batteries with pucherite as electrode material.Based on the above fact, this
Invention proposes a kind of new pucherite/nickel hydroxide secondary alkaline batteries and preparation method thereof.
Content of the invention
It is an object of the invention to provide a kind of new pucherite/nickel hydroxide secondary alkaline batteries and its preparation side
Method.
The technical scheme is that：
A kind of pucherite/nickel hydroxide secondary alkaline batteries, it is characterised in that with nickel hydroxide material as positive pole, vanadic acid
Bismuth material is negative pole, and it is 0.5～1.5V that alkaline aqueous solution is electrolyte, voltage window.
Described nickel hydroxide material, including following component by mass percentage：Nickel element 48～63%, cobalt element
0.5～12%, zinc element 0.5～6.5%, Ce elements 0～8.5%, balance of hydrogen, oxygen；The apparent density of nickel hydroxide material
For 1.58～1.75g/cm3, tap density be 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm 2.0～2.5g/cm3；Its specific surface area is 5～100m2/ g, the particle diameter of material is 1
～15 μm.
Described pucherite material, be in organic solvent system, by chemical precipitation method, solvent-thermal method and chemistry
The method combined with solvent-thermal method by the sedimentation method is prepared, and its specific surface area is 10～500m2/g；Its preparation method includes as follows
Step：
(1) bismuth raw material will be contained to be dissolved in solvent, will be configured to the bismuth ion solution that concentration is 0.01～5mol/L；By solubility
Vanadate be dissolved in solvent, be made into the vanadic acid radical ion solution that concentration is 0.01～5mol/L；
(2) mol ratio for pressing bismuth with vanadium is (1:0.9)～(1:1.2), vanadic acid radical ion solution is added drop-wise to step (1)
In bismuth ion solution, stirring or ultrasound are uniformly mixed so as to obtain golden transparent mixed solution, then are 5～50 DEG C and stirring condition in temperature
Lower to mixed solution and dripping basic organic solution carry out 0.5～10h of precipitation, control endpoint pH be 5～12, reacted
After becoming will precipitation deionized water, dehydrated alcohol are washed successively and carry out solid-liquid separation respectively, by the solidss for obtaining in 60～
6～36h is dry at 150 DEG C prepares pucherite material；
Or above-mentioned golden transparent mixed solution is transferred in teflon-lined autoclave, 100
Carry out 1～24h of solvent thermal reaction, then deionized water, absolute ethanol washing precipitated successively, and carry out solid-liquid at～250 DEG C dividing
From at 60～150 DEG C, dry 6～36h obtains pucherite material；
Or be (1 by the mol ratio of bismuth and vanadium:0.9)～(1:1.2), vanadic acid radical ion solution is added drop-wise to step (1)
Bismuth ion solution in, stirring or ultrasound are uniformly mixed so as to obtain golden transparent mixed solution, then temperature be
It is 5～12, to obtain 0.5～10h of precipitation, control endpoint pH to be carried out to mixed solution and dripping basic organic solution under part
Reactant mixture, then this reactant mixture is transferred in teflon-lined autoclave, at 100～250 DEG C
Carry out 1～24h of solvent thermal reaction, then deionized water, absolute ethanol washing precipitation successively, and solid-liquid separation is carried out, in 60～
6～36h is dry at 150 DEG C obtains pucherite material.
Further, described containing bismuth raw material include bismuth metal, bismuth oxide, Bismuth hydrate., waltherite, bismuth subcarbonate,
One or more in sulphuric acid oxygen bismuth, novismuth, bismuth sulfate, bismuth nitrate, halogenation bismuth, bismuth acetate；For can not be direct
Be dissolved in the solvent containing bismuth raw material through being chemically converted to solubility containing bismuthide.
Further, described vanadate, the vanadate including solubility or metavanadate.
Further, described basic organic solution is dissolved in the solution that organic solvent is obtained, Huo Zheyou for alkali inorganic substance
Machine aqueous slkali, the concentration of alkali is 0.01～5mol/L；The monohydric alcohol of preferred alkali metal hydroxide or polyhydric alcohol solutions, or three second
The solution such as hydramine, ethylenediamine, triethylamine, n-butylamine.
Further, described solvent, including one or two in ethylene glycol, glycerol.
The preparation method of above-mentioned pucherite/nickel hydroxide secondary alkaline batteries, comprises the steps：
(1) preparation of vanadic acid bismuth pole and nickel hydroxide electrode
Vanadic acid bismuth pole：By pucherite material 70～95%, conductive agent 3～15%, binding agent 2～15% percent mass
Than weighing, first binding agent is dissolved in METHYLPYRROLIDONE, is made into the solution of 0.01～0.04g/ml, then by vanadic acid
Bismuth material, conductive agent are added in binder solution, are evenly stirred until paste, and coating on a current collector, then is placed on drying
80～150 DEG C of 5～36h of drying in case, are cut into electrode slice after roll-in, that is, obtain pucherite electrode slice；
Nickel hydroxide electrode：According to nickel hydroxide material 70～95%, conductive agent 3～15%, binding agent 2～15% matter
Amount percentage ratio weighing is standby, then successively binding agent, conductive agent, nickel hydroxide material mix homogeneously is tuned into pasty state and is applied in bubble
On foam nickel, 80～150 DEG C of 5～36h of drying, nickel hydroxide electrode piece is obtained after roll-in cutting；
(2) preparation of pucherite/nickel hydroxide secondary alkaline batteries
Nickel hydroxide electrode piece, barrier film, pucherite electrode slice are sequentially placed in battery mould and are configured to the three of two electrodes
Mould fit sealing is configured to battery after Deca alkaline aqueous electrolyte by Mingzhi's structure.
Further, described binding agent is Kynoar (PVDF), politef (PTFE), carboxymethyl cellulose
One or more in sodium (CMC), butadiene-styrene rubber (SBR)；Described conductive agent is acetylene black, white carbon black, graphite or graphite
One or more in alkene；Described collector is the holey such as steel mesh, nickel foam, Copper Foil, foil-like or textile-like
One or more in high electronic conductivity material.
Further, described barrier film be graft polypropylene non-woven fabrics, graft PP microporous membrane, all-glass paper, nylon no
Spin cloth, polyvinyl alcohol film, one or more in asbestos paper；Described electrolyte is one or more alkali metal hydrogens
The aqueous solution of oxide, its concentration is 1～8mol/L.
The structure of prepared material and electrochemical property test
Using 3020 type specific surface area of TriStar II and pore-size distribution instrument, the pucherite material prepared by the present invention is entered
Row test；Using JEOLJEM-3010 type scanning electron microscope to prepared by the nickel hydroxide material that used and the present invention
Pucherite material carries out microscopic appearance test；Using D/MAX-3C type Powder X-ray Diffractometer to prepared pucherite material
Carry out the test of crystal phase structure.
Using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, the new Weir Electronics Co., Ltd. life in Shenzhen
The BTS-3000 cell tester of product is circulated volt-ampere, constant current to the pucherite/nickel hydroxide secondary alkaline batteries for preparing and fills
The electrochemical property tests such as electric discharge, cycle life.
The beneficial effects of the present invention is：
(1) present invention is prepared for pucherite electrode material, and itself and nickel hydroxide are configured to a kind of new pucherite/hydrogen
Nickel oxide secondary alkaline batteries, the voltage window of battery is 0.5～1.5V, and the specific capacity when electric current density is for 1A/g is
201.9mAh/g, the specific capacity when electric current density is for 2A/g is 178.5mAh/g, and after circulating 500 times, specific capacity maintains 81%
More than.
(2) present invention has preparation process is simple, environmental friendliness, the secondary alkaline electro of the pucherite/nickel hydroxide for being constructed
The features such as pond has that specific capacity is high, has extended cycle life, cost performance is high, is a kind of alkali secondary chemistry with broad prospect of application
Power supply.
Description of the drawings
Fig. 1 is the X-ray diffractogram of pucherite prepared by embodiment 1.
Fig. 2 is used the scanning electron microscope diagram of nickel hydroxide by embodiment 1～4.
Fig. 3 is pucherite prepared by embodiment 1/perseverance of the nickel hydroxide secondary alkaline batteries under 1～5A/g electric current density
Stream discharge curve.
Fig. 4 is the scanning electron microscope (SEM) photograph of pucherite prepared by embodiment 2.
Fig. 5 is pucherite/nickel hydroxide secondary alkaline batteries prepared by embodiment 2 under 5～50mv/s sweep speed
Cyclic voltammogram.
Fig. 6 is the nitrogen Adsorption and desorption isotherms of pucherite prepared by embodiment 3.
Fig. 7 is circulation longevity of the pucherite/nickel hydroxide secondary alkaline batteries under 1A/g electric current density prepared by embodiment 3
Life and coulombic efficiency figure.
Fig. 8 is circulation volt of the pucherite/nickel hydroxide secondary alkaline batteries prepared by embodiment 4 under the different scanning cycle
Peace test chart.
Specific embodiment
Below technical scheme is further illustrated with specific embodiment, but the invention is not limited in embodiment.
Embodiment 1
(1) take 5mmol bismuth nitrate to be dissolved in 10ml ethylene glycol, magnetic agitation obtains the nothing of 0.05mol/L to being completely dissolved
Color clear solution；Take 5mmol ammonium metavanadate and 10ml ethylene glycol wiring solution-forming is dissolved in, then which is mixed with bismuth nitrate solution, obtain mixed
Close solution.
(2) the sodium hydroxide ethylene glycol solution for taking concentration for 1mol/L is added drop-wise in above-mentioned mixed solution, is continued under room temperature
Stirring 1h, control endpoint pH is 8, to obtain yellow mercury oxide.Gained precipitate with deionized water, dehydrated alcohol are washed successively and are gone forward side by side
Products therefrom is finally vacuum dried 18h at 80 DEG C and prepares pucherite material by row solid-liquid separation.
(3) using XRD-6000 type x-ray diffractometer, pucherite material manufactured in the present embodiment is tested, such as Fig. 1
Shown, sample is in 2 θ=15.1 °, and 18.6 °, 18.9 °, 28.9 °, 30.5 °, 34.5 °, 35.2 °, 39.8 °, the positions such as 42.3 ° are equal
There is obvious characteristic peak, consistent with standard card (JCPDS No.14-6088), crystal face corresponding to which is respectively 020,
110、011、121、040、200、002、211、150.
(4) nickel hydroxide material for embodiment 1～4 being adopted using JEOLJEM-3010 type scanning electron microscope is entered
Row test, as shown in Fig. 2 the nickel hydroxide material is about 5～15 μm of microsphere pattern, micron bulb diameter.
(5) according to pucherite material 80% manufactured in the present embodiment, conductive agent 10%, binding agent 10% mass percent
Weighing is standby, dissolves binding agent PVDF with appropriate METHYLPYRROLIDONE first, then sequentially adds conductive agent acetylene
Black, pucherite material is tuned into pasty state and is applied in nickel foam respectively, 100 DEG C of drying 12h, obtains pucherite electrode slice after roll-in.
Mass percent according to nickel hydroxide material 80%, conductive agent 10%, binding agent 10% weighs standby, Ran Houyi
Secondary PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material mix homogeneously are tuned into pasty state and are applied in nickel foam,
100 DEG C of drying 12h, obtain nickel hydroxide electrode piece after roll-in cutting.
(6) nickel hydroxide electrode piece/barrier film/pucherite electrode slice is sequentially placed in special battery mould and is configured to two
The sandwich structure of electrode, then the KOH electrolyte of Deca 6mol/L, then by battery mould fit sealing, that is, are assembled into described
Pucherite/nickel hydroxide secondary alkaline batteries.
(7) using Shanghai Chen Hua company production CHI660A electrochemical workstation, to pucherite manufactured in the present embodiment/
Nickel hydroxide secondary alkaline batteries carry out constant current charge-discharge test at room temperature.Fig. 3 is the discharge curve under different electric current densities,
When electric current density is for 1A/g, specific capacity is 201.9mAh/g；Specific capacity 178.5mAh/g when electric current density is for 2A/g；In electricity
Current density is specific capacity 166mAh/g during 2A/g；Specific capacity 145.6mAh/g when electric current density is for 5A/g, the electricity of discharge curve
Flattening bench is 0.6～0.9V.
Embodiment 2
(1) take in the mixed solvent that 5mmol bismuth chloride is dissolved in 10ml ethylene glycol and 10ml glycerol composition, magnetic agitation is extremely
It is completely dissolved, obtains the colourless transparent solution of 0.05mol/L；Take 5.25mmol ammonium metavanadate and be dissolved in 10ml ethylene glycol and 10ml third
Wiring solution-forming in the mixed solvent of triol composition, then which is mixed with bismuth chloride solution, obtain mixed solution.
(2) above-mentioned mixed solution is transferred in teflon-lined autoclave, at 140 DEG C, reacts 4h.Will
Gained precipitate with deionized water, dehydrated alcohol are washed successively and carry out solid-liquid separation, finally by products therefrom at 90 DEG C vacuum
Dry 12h and prepare pucherite material.
(3) using JEOLJEM-3010 type scanning electron microscope, pucherite material manufactured in the present embodiment is surveyed
Examination, as shown in figure 4, the pucherite material is in rod, length is 0.5～3 μm.
(4) with (5) respectively with (5) and (6) step in embodiment 1.
(6) using Shanghai Chen Hua company production CHI660A electrochemical workstation, to pucherite manufactured in the present embodiment/
Nickel hydroxide secondary alkaline batteries are circulated volt-ampere test at room temperature, and voltage window is that 0.5～1.5V, prepared battery exists
Under different scanning rates (5,10,20,50mV/s) cyclic voltammetry curve as shown in figure 5, as can be seen from the figure oxidation peak exist
1.0～1.2V scope, reduction peak are in 0.8～0.9V scope.
Embodiment 3
(1) take 5mmol bismuth nitrate to be dissolved in 15ml ethylene glycol, obtain the colourless transparent solution of 0.05mol/L；Take 5mmol
Sodium metavanadate is dissolved in 15ml ethylene glycol wiring solution-forming, then by itself and bismuth nitrate solution stirring and evenly mixing, obtains mixed solution.
(2) ethanol solution for taking concentration for the triethanolamine of 2mol/L is added drop-wise in above-mentioned mixed solution, is continued under room temperature
Stirring 2h, control endpoint pH is 9, to obtain yellow mercury oxide.
(3) gained precipitation is washed successively with dehydrated alcohol, deionized water and solid-liquid separation is carried out, finally by products therefrom
12h is vacuum dried at 90 DEG C and prepares pucherite material.
(4) using 3020 type specific surface area of TriStar II and pore-size distribution instrument to pucherite material manufactured in the present embodiment
Material is tested, and learns that the specific surface area of the pucherite material is 10.78m2/g.As seen from Figure 6, the isothermal adsorption desorption of the sample
Curve is IV class isothermal adsorption desorption curve, illustrates the sample for mesoporous solid.Hysteresis loop is H3 type hysteresis loop, illustrates that sample is main
There is slit-like hole.
(5) according to pucherite material 75% manufactured in the present embodiment, conductive agent 15%, binding agent 10% mass percent
Weighing is standby, dissolves binding agent PVDF with appropriate METHYLPYRROLIDONE first, then sequentially adds conductive agent acetylene
Black, pucherite material is tuned into pasty state and is applied in nickel foam respectively, 100 DEG C of drying 12h, obtains pucherite electrode slice after roll-in.
Standby according to the mass percent weighing of nickel hydroxide material 90%, conductive agent 5%, binding agent 5%, then successively
PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material mix homogeneously are tuned into pasty state and are applied in nickel foam, 100
DEG C dry 12h, obtain nickel hydroxide electrode piece after roll-in cutting.
(6) nickel hydroxide electrode piece/barrier film/pucherite electrode slice is sequentially placed in special battery mould and is configured to two
Then battery mould is fastened by the sandwich structure of electrode, then Deca 5mol/L KOH and 0.5mol/L LiOH mixed electrolytic solution
Sealing, that is, be assembled into described pucherite/nickel hydroxide secondary alkaline batteries.
(7) using the BTS-3000 cell tester of the new Weir Electronics Co., Ltd. production in Shenzhen, voltage window is 0.5
Pucherite manufactured in the present embodiment/nickel hydroxide secondary alkaline batteries are circulated life test by～1.5V at room temperature.Such as
Shown in Fig. 7, battery after 500 constant current charge-discharge circulations, still keeps initial specific capacity under the electric current density of 2A/g
81%, coulombic efficiency is maintained at more than 95%.
Embodiment 4
(1) take 5mmol bismuth nitrate to be dissolved in 10ml glycerol, magnetic agitation obtains the nothing of 0.05mol/L to being completely dissolved
Color clear solution；Take 5mmol sodium metavanadate and 10ml ethylene glycol wiring solution-forming is dissolved in, then which is mixed with bismuth nitrate solution, obtain mixed
Close solution.
(2) glycerin solution for taking concentration for the potassium hydroxide of 1mol/L is added drop-wise in above-mentioned mixed solution, is held under room temperature
Continuous stirring 1h, control endpoint pH is 11, to obtain yellow suspension thing.
(3) above-mentioned float is transferred in teflon-lined autoclave, at 160 DEG C, reacts 1h.By institute
Precipitate with deionized water, dehydrated alcohol are washed successively and carry out solid-liquid separation, finally by products therefrom, vacuum is done at 90 DEG C
Dry 12h prepares pucherite material.
(4) according to pucherite material 85% manufactured in the present embodiment, conductive agent 10%, binding agent 5% mass percent
Weighing is standby, dissolves binding agent PVDF with appropriate METHYLPYRROLIDONE first, then sequentially adds conductive agent acetylene
Black, pucherite material is tuned into pasty state and is applied in nickel foam respectively, 100 DEG C of drying 12h, obtains pucherite electrode slice after roll-in.
Mass percent according to nickel hydroxide material 85%, conductive agent 10%, binding agent 5% weighs standby, Ran Houyi
Secondary PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material mix homogeneously are tuned into pasty state and are applied in nickel foam,
100 DEG C of drying 12h, obtain nickel hydroxide electrode piece after roll-in cutting.
(5) nickel hydroxide electrode piece/barrier film/pucherite electrode slice is sequentially placed in special battery mould and is configured to two
The sandwich structure of electrode, then the KOH electrolyte of Deca 5mol/L, then by battery mould fit sealing, that is, are assembled into described
Pucherite/nickel hydroxide secondary alkaline batteries.
(6) using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, the pucherite to the present embodiment construction/
Nickel hydroxide secondary alkaline batteries are circulated volt-ampere test at room temperature, and voltage window is that 0.5～1.5V, sweep speed is
50mV/s.Prepared battery under the different scanning cycle (first, ten, 20 times) cyclic voltammetry curve as shown in figure 8, its oxygen
Change peak-to-peak position is 1.1V, and reduction peak peak position is 0.8V, as seen from the figure the oxidation peak under different cycle periods and reduction peak peak position
Be basically unchanged, cyclic voltammetry curve favorable reproducibility, this shows that the battery has good circulating and reversible stability.
Claims (10)
1. a kind of pucherite/nickel hydroxide secondary alkaline batteries, it is characterised in that：It is negative pole, hydroxide using pucherite material
Nickel material is positive pole, and it is 0.5～1.5V that aqueous slkali is the voltage window of electrolyte solution, battery.
2. pucherite according to claim 1/nickel hydroxide secondary alkaline batteries, it is characterised in that：Described hydroxide
Nickel material, including following component by mass percentage：Nickel element 48～63%, cobalt element 0.5～12%, zinc element 0.5
～6.5%, Ce elements 0～8.5%, balance of hydrogen, oxygen；The apparent density of nickel hydroxide material is 1.58～1.75g/cm3, shake
Real density is 2.0～2.5g/cm3；The specific surface area of material is 5～100m2/ g, particle diameter are 1～15 μm.
3. pucherite according to claim 1 and 2/nickel hydroxide secondary alkaline batteries, it is characterised in that described vanadic acid
Bismuth material, is in organic solvent system, is tied by chemical precipitation method, solvent-thermal method and chemical precipitation method and solvent-thermal method
The method of conjunction is prepared, and its specific surface area is 10～500m2/g；Its preparation method comprises the steps：
(1) bismuth raw material will be contained to be dissolved in solvent, will be configured to the bismuth ion solution that concentration is 0.01～5mol/L；Vanadium by solubility
Hydrochlorate is dissolved in solvent, is made into the vanadic acid radical ion solution that concentration is 0.01～5mol/L；
(2) mol ratio for pressing bismuth with vanadium is (1:0.9)～(1:1.2), vanadic acid radical ion solution is added drop-wise to the bismuth of step (1) from
In sub- solution, stirring or ultrasound are uniformly mixed so as to obtain golden transparent mixed solution, then temperature be under 5～50 DEG C and stirring condition to
It is 5～12 that mixed solution and dripping basic organic solution carries out 0.5～10h of precipitation, control endpoint pH, after the completion of reaction
By precipitation, deionized water, dehydrated alcohol are washed successively and carry out solid-liquid separation respectively, by the solidss for obtaining in 60～150 DEG C
Lower 6～36h of drying prepares pucherite material；
Or above-mentioned golden transparent mixed solution is transferred in teflon-lined autoclave, 100～250
1～24h of solvent thermal reaction, then deionized water, absolute ethanol washing precipitation successively is carried out at DEG C, and carries out solid-liquid separation, in
6～36h is dry at 60～150 DEG C obtains pucherite material；
Or be (1 by the mol ratio of bismuth and vanadium:0.9)～(1:1.2), vanadic acid radical ion solution be added drop-wise to the bismuth of step (1)
In solion, stirring or ultrasound are uniformly mixed so as to obtain golden transparent mixed solution, then in temperature under 5～50 DEG C and stirring condition
It is 5～12, to be reacted 0.5～10h of precipitation, control endpoint pH to be carried out to mixed solution and dripping basic organic solution
Mixture, then this reactant mixture is transferred in teflon-lined autoclave, carry out at 100～250 DEG C
1～24h of solvent thermal reaction, then deionized water, absolute ethanol washing precipitation successively, and solid-liquid separation is carried out, in 60～150 DEG C
Lower 6～36h of drying obtains pucherite material.
4. pucherite according to claim 3/nickel hydroxide secondary alkaline batteries, it is characterised in that described bismuth-containing original
Material includes bismuth metal, bismuth oxide, Bismuth hydrate., waltherite, bismuth subcarbonate, sulphuric acid oxygen bismuth, novismuth, bismuth sulfate, nitric acid
One or more in bismuth, halogenation bismuth, bismuth acetate；For being directly dissolved in, passing through containing bismuth raw material for the solvent is chemical
Be converted into solubility containing bismuthide.
5. pucherite according to claim 3/nickel hydroxide secondary alkaline batteries, it is characterised in that described vanadate,
Vanadate or metavanadate including solubility.
6. pucherite according to claim 3/nickel hydroxide secondary alkaline batteries, it is characterised in that described alkalescence has
Machine solution is dissolved in the solution that organic solvent is obtained, or organic alkali solution for alkali inorganic substance, and the concentration of alkali is 0.01～5mol/L.
7. pucherite according to claim 3/nickel hydroxide secondary alkaline batteries, it is characterised in that described solvent, bag
Include ethylene glycol, one or two in glycerol.
8. the preparation method of the pucherite described in any one of claim 1 to 7/nickel hydroxide secondary alkaline batteries, its feature exists
In：
(1) preparation of vanadic acid bismuth pole and nickel hydroxide electrode
Vanadic acid bismuth pole：Claim by the mass percent of pucherite material 70～95%, conductive agent 3～15%, binding agent 2～15%
Amount, is dissolved in binding agent in METHYLPYRROLIDONE first, is made into the solution of 0.01～0.04g/ml, then by pucherite material
Material, conductive agent are added in binder solution, are evenly stirred until paste, are coated on a current collector, then by which at 80～150 DEG C
5～36h being dry in drying baker, electrode slice is cut into after roll-in, that is, obtains pucherite electrode slice；
Nickel hydroxide electrode：According to nickel hydroxide material 70～95%, conductive agent 3～15%, binding agent 2～15% quality hundred
Divide ratio to weigh standby, then successively binding agent, conductive agent, nickel hydroxide material mix homogeneously are tuned into pasty state and are applied in nickel foam
On, 80～150 DEG C of 5～36h of drying, nickel hydroxide electrode piece is obtained after roll-in cutting；
(2) preparation of pucherite/nickel hydroxide secondary alkaline batteries
Nickel hydroxide electrode piece, barrier film, pucherite electrode slice are sequentially placed in battery mould the sandwich for being configured to two electrodes
Structure, by mould fit sealing after Deca alkaline aqueous electrolyte.
9. the preparation method of pucherite according to claim 8/nickel hydroxide secondary alkaline batteries, it is characterised in that institute
The binding agent that states is Kynoar, politef, sodium carboxymethyl cellulose, one or more in butadiene-styrene rubber；
Described conductive agent is one or more in acetylene black, white carbon black, graphite or Graphene；Described collector is porous web
The high electronic conductivity material of shape, foil-like or textile-like, is related to nickel foam, nickel foil or nickel screen, copper mesh or Copper Foil, rustless steel
In net, rustless steel Punching steel strip or stainless steel foil, titanium foil or titanium net, lead foil or lead cloth, graphitization carbon cloth or Graphene cloth material
One or more.
10. the preparation method of pucherite according to claim 8/nickel hydroxide secondary alkaline batteries, it is characterised in that institute
The barrier film that states is graft polypropylene non-woven fabrics, graft PP microporous membrane, all-glass paper, nylon nonwoven fabrics, polyvinyl alcohol film, asbestos
One or more in paper；Described electrolyte is the aqueous solution of one or more alkali metal hydroxides, and which is dense
Spend for 1～8mol/L.
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| CN111215066B (en) * | 2020-02-22 | 2021-08-24 | 青岛科技大学 | Pt/BiVO4/Bi2O3Photo-assisted preparation method of catalyst and application of photo-assisted preparation method to photoelectrocatalysis |
| CN113571717A (en) * | 2021-07-23 | 2021-10-29 | 中国人民解放军军事科学院军事医学研究院 | High-efficiency photoelectrode and preparation method and application thereof |
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