CN106450287B - A kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and preparation method thereof - Google Patents
A kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and preparation method thereof Download PDFInfo
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- CN106450287B CN106450287B CN201610940415.6A CN201610940415A CN106450287B CN 106450287 B CN106450287 B CN 106450287B CN 201610940415 A CN201610940415 A CN 201610940415A CN 106450287 B CN106450287 B CN 106450287B
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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
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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention discloses a kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and preparation method thereof.Using nickel hydroxide as cell positive material, bismuth oxyfluoride be cell negative electrode material, alkaline aqueous solution is electrolyte.The bismuth oxyfluoride the preparation method comprises the following steps: soluble bismuth raw material be dissolved in solvent or insoluble bismuth raw material is dissolved in acid being configured to bismuth ion solution；Or the bismuth raw material that solubility product is greater than bismuth oxyfluoride solubility product is added to the solidliquid mixture that bismuth-containing is made into solvent；Or a certain amount of regulator is added into bismuth-containing system again；Or a certain amount of carbon materials are added into bismuth-containing system again；Then a certain amount of fluoride solution reaction is added in bismuth-containing system and generates bismuth oxyfluoride；Prepared bismuth oxyfluoride is made of the nanometer sheet of 3~30nm.Specific capacity of the battery that the present invention is constructed when current density is 0.5A/g is 227mAh/g.Simple, environmental-friendly, battery the excellent electrochemical performance of preparation process of the invention.
Description
Technical field
The invention belongs to electrochemical energy storage field, in particular to a kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and
Preparation method.
Background technique
Resource problem is prominent since 21 century, and the research of efficient green energy storage device is more particularly important.Therefore, it can follow
The secondary cell that ring uses has irreplaceable status in new energy field, supports the progress of sustainable development.With
The rapid development of portable electronic product and universal, a variety of small sizes that have been born, lightweight, high capacity, the long-life novel two
Primary cell, and its market prospects is very considerable, therefore constantly research and development new secondary battery is particularly important.New electricity
Pool concept, electrode material, the exploration of battery system and research are the power producer that battery technology is constantly progressive, even more energy storage field
The hot spot of research.
Traditional secondary alkaline battery mainly has nickel/cadmium cell, the nickel iron battery, nickel/hydrogen battery, nickel zinc that anode is done with nickel
Battery etc..Nickel/cadmium cell is stablized durable, but the toxicity of main raw material(s) component cadmium is big, at high cost, pollutes environment.Nickel iron battery
Self-discharge rate is high, poor performance at low temperatures.Nickel/hydrogen battery charging time is longer than nickel-cadmium cell, and the self discharge time increases with temperature and increased
Greatly.Nickel zinc battery zinc electrode crystalline form, which changes, to be formed dendrite the service life is caused to be deteriorated.In consideration of it, the proposition of novel secondary alkaline battery
It is particularly important with research.
Bismuthino toxicity of compound is small, at low cost, grinds in catalyst, gas sensor, electrode material, optical material
Study carefully application.Bismuth hydroxide, bismuth oxide, bismuth ferrite, bismuth molybdate, bismuth oxide etc. or they and graphene, nano titania
The composite material of pipe, polyaniline, manganese dioxide etc., which is used as electrode material, research.
Xia etc. [ECS Transactions 28 (2010): 125] is prepared for bismuth oxide nanometer sheet by chemical precipitation method
For electrochemical capacitor, specific capacity is 996F g-1, only decayed 4.2% after 1000 charge and discharge cycles.Ma etc.
[a kind of flower-shaped (BiO) 103] Electrochimica Acta 168 (2015): is prepared for by hydro-thermal method2CO3@MnO2With
Bi2O3@MnO2The nano-complex of core-shell structure is simultaneously applied to supercapacitor, and specific capacity is respectively 196F g-1With
139.4F g-1, and be initial capacity 125% and 112% after 1000 charge and discharge cycles.[the Electrochimica such as Nie
Acta 154 (2015): 30] preparing bismuth sulfide/graphene composite material by simple hydro-thermal reaction, and then has studied its capacitor
Performance.Liu et al. [Journal of The Electrochemical Society 159 (2012): 586] heavy by electrochemistry
Product combines the mode of heat treatment to be prepared for the molybdic acid bismuth nano-wire of high-specific surface area and have studied its answering in supercapacitor
With.Kang etc. [Journal of Power Sources 195 (2010): 2023] has studied the Li of BiOF cladding
[Ni0.5Mn1.5]O4Application in rechargeable lithium battery.[the Journal of Materials Chemistry 19 such as Lee
(2009): 1995] having studied the Li [Li of BiOF cladding0.1Al0.05Mn1.85]O4Double action in lithium battery, 100 circulations
The 96.1% of initial capacity is still kept afterwards, is primarily due to BiOF and is reduced electrolyte LiPF6The infiltration of the HF generated is decomposed, and
At 55 DEG C, capacity is higher.
Patent of invention [application publication number CN104148094A] discloses a kind of " bismuth oxyfluoride/graphene composite visible light
The preparation method of catalyst ", the invention spent glycol dissolve bismuth nitrate and sodium fluoride respectively, are prepared for one kind by precipitating reagent of water
Bismuth oxyfluoride/graphene composite visible light catalyst.
Patent of invention [application publication number CN104891444A], which discloses, " a kind of method for preparing BiOF photochemical catalyst and urges
Agent effect ".The patent, using bismuth nitrate and hydrofluoric acid as raw material, is prepared for using tetrahydrofuran as solvent by hydro-thermal reaction
BiOF photochemical catalyst.
It is related to using yet there are no as research of the electrode material in terms of secondary alkaline batteries about bismuth oxyfluoride at present
Report.Based on the above fact, the invention proposes a kind of novel bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and its preparation
Method.
Summary of the invention
It is an object of the invention to propose a kind of novel bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries and its preparation side
Method.
The technical solution of the present invention is as follows:
A kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries, using bismuth oxyfluoride material as the negative electrode active material of battery,
Using nickel hydroxide material as the positive electrode active materials of battery, using aqueous slkali as electrolyte solution, the voltage window of battery is 0.4~
1.3V。
The mass percent of contained element is nickel 48~63%, cobalt 0.5~12%, zinc in the nickel hydroxide material
0.5~6.5%, cerium 0~8.5%, remaining be the nonmetalloids such as hydrogen, oxygen；The specific surface area of nickel hydroxide material be 5~
100m2/ g, partial size are 1~15 μm, the apparent density of material is 1.58~1.75g/cm3, material tap density be 2.0~
2.5g/cm3。
The bismuth oxyfluoride electrode material by being constituted with a thickness of the nanometer sheet of 3~30nm, specific surface area be 10~
500m2/g.Preparation method includes the following steps:
(1) soluble bismuth raw material is dissolved in solvent, is configured to the bismuth ion solution that concentration is 0.01~5mol/L；
Alternatively, insoluble bismuth raw material is dissolved in acid, it is configured to the bismuth ion solution that concentration is 0.01~5mol/L；
Alternatively, the bismuth raw material that solubility product constant is greater than bismuth oxyfluoride solubility product constant is added in solvent, it is configured to bismuth original
Expect that solid content is the solid-liquid mixtures of 5~200g/L；(for convenience of following expression, bismuth raw material solid content herein is 5~200g/
The solid-liquid mixtures and bismuth ion solution of L, Unified Expression are bismuth-containing solution)
Alternatively, a certain amount of regulator is added in above-mentioned bismuth-containing solution again, the addition quality of table regulator is bismuth raw material
The 0.1%~50% of quality；
Alternatively, a certain amount of carbon materials are added in above-mentioned bismuth-containing solution again, the addition quality of carbon materials is that bismuth is former
Expect the 1%~10% of quality；
(2) soluble fluoride is dissolved in solvent, is made into the fluoride solution that concentration is 0.01~5mol/L；
(3) it is (1:0.9)~(0.9:1) by the molar ratio of bismuth and fluorine, fluoride solution is added drop-wise to the bismuth-containing of step (1)
In solution, 0 DEG C~60 DEG C at a temperature of reacted using stirring or ultrasound, react and use precipitating respectively after 0.5~10h
Deionized water, dehydrated alcohol successively wash repeatedly, and are separated by solid-liquid separation, and obtained solid matter is done at 60~150 DEG C
Dry 6~36h prepares bismuth oxyfluoride material.
Further, the bismuth raw material includes bismuth metal, bismuth oxide, bismuth hydroxide, waltherite, basic bismuth carbonate, sulphur
One or more of sour oxygen bismuth, novismuth, bismuth sulfate, bismuth nitrate, halogenation bismuth, bismuth acetate；The solvent includes
It is water, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, ethylene glycol, glycerine, triethanolamine, polyethylene glycol, diethylene glycol (DEG), three sweet
One or more of alcohol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether；The acid includes inorganic acid and has
Machine acid, one or more of preferably sulfuric acid, nitric acid, hydrochloric acid, acetic acid, benzoic acid, phenylacetic acid, dodecyl benzene sulfonic acid；
The fluoride include one or both of hydrofluoric acid, ammonium fluoride, sodium fluoride, sodium bifluoride, potassium fluoride, potassium hydrogen fluoride with
On.
Further, the regulator is dodecyl sodium sulfate, polyvinyl pyrrolidone, OP-10 emulsifier, lemon
One or more of sour sodium, sodium salicylate, sodium tartrate, cetyl trimethylbenzene ammonium bromide, polyvinyl alcohol.
The carbon materials are one or more of acetylene black, activated carbon, graphitized carbon, graphene.
Above-mentioned bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries preparation method, includes the following steps:
(a) preparation of bismuth oxyfluoride electrode and nickel hydroxide electrode
Bismuth oxyfluoride electrode: by the quality of bismuth oxyfluoride material 70~95%, conductive agent 3~15%, binder 2~15%
Percentage weighs, and binder is dissolved in n-methyl-2-pyrrolidone first, is made into the solution of 0.01~0.04g/ml, then will
Bismuth oxyfluoride material, conductive agent are added in binder solution, are evenly stirred until paste, coating on a current collector, then by its
Dry 5~36h in 80~150 DEG C of drying box is cut into electrode slice after roll-in to get bismuth oxyfluoride electrode slice is arrived；
Nickel hydroxide electrode: according to the matter of nickel hydroxide material 70~95%, conductive agent 3~15%, binder 2~15%
It measures percentage and weighs spare, then successively binder, conductive agent, nickel hydroxide material are uniformly mixed and are tuned into paste and are applied to bubble
On foam nickel, 80~150 DEG C of dry 5~36h obtain nickel hydroxide electrode piece after roll-in and cutting.
(b) bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries preparation
Nickel hydroxide electrode piece, diaphragm, bismuth oxyfluoride electrode slice are sequentially placed into and are configured to two electrodes in battery mould
Sandwich structure is added dropwise after alkaline aqueous electrolyte mold fit sealing being configured to battery.
Further, the binder be Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE) lotion, carboxymethyl it is fine
Tie up one or more of plain sodium (CMC), butadiene-styrene rubber (SBR)；The conductive agent is acetylene black, carbon black, graphite, stone
One or more of black alkene；The collector is holeys, foil-like or the textile-likes such as steel mesh, nickel foam, copper foil
One or more of high electronic conductivity material.
Further, the diaphragm be grafting polypropylene non-woven fabrics, graft PP microporous barrier, all-glass paper, nylon without
One or more of woven fabric, polyvinyl alcohol film, asbestos paper；The electrolyte is one or more kinds of alkali metal
Oxyhydroxide, concentration are 1~8.0mol/L；Also include in electrolyte one of potassium fluoride, sodium fluoride or ammonium fluoride or
Two or more assisted electrolysis matter, the concentration of assisted electrolysis matter are 0.05~6mol/L.
The structure and electrochemical property test of material prepared
Using 3020 type specific surface area of TriStar II and pore-size distribution instrument to bismuth oxyfluoride material prepared by the present invention
It is tested；Using JEOLJEM-3010 type scanning electron microscope to prepared by used nickel hydroxide material and the present invention
Bismuth oxyfluoride material carry out microscopic appearance test；Prepared fluorine is aoxidized using D/MAX-3C type Powder X-ray Diffractometer
The test of bismuth material progress crystal phase structure.
It is raw using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, new Weir Electronics Co., Ltd., Shenzhen
The BTS-3000 cell tester of production carries out cyclic voltammetric, constant current to bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries of preparation
The electrochemical property tests such as charge and discharge, cycle life.
The beneficial effects of the present invention are:
(1) present invention is prepared for bismuth oxyfluoride by simple process, and itself and ball-shape nickel hydroxide are configured to one kind newly
The bismuth oxyfluoride of type/nickel hydroxide secondary alkaline batteries, the voltage window of battery are 0.4~1.3V, are 0.5A/ in current density
Specific capacity when g is 227mAh/g, and the specific capacity when current density is 1A/g is 189.5mAh/g, specific volume after circulation 500 times
Amount maintains 87% or more.
(2) present invention has preparation process simple, environmental-friendly, the secondary alkalinity of bismuth oxyfluoride/nickel hydroxide constructed
Battery has the characteristics that specific energy and specific power are high, has extended cycle life, cost performance is high, is a kind of with the new of broad prospect of application
Type secondary chemical sources of electric energy.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of bismuth oxyfluoride prepared by embodiment 1.
Fig. 2 uses the scanning electron microscope diagram of nickel hydroxide by embodiment 1.
Fig. 3 is the X-ray diffractogram of bismuth oxyfluoride prepared by embodiment 2.
Fig. 4 is the isothermal nitrogen adsorption desorption curve of bismuth oxyfluoride prepared by embodiment 3.
Fig. 5 is bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries prepared by embodiment 1 in 0.5~10A/g current density
Under constant current charge-discharge diagram.
Fig. 6 is bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries prepared by embodiment 2 in 5~50mv/s sweep speed
Under cyclic voltammogram.
Fig. 7 is bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries following under 2A/g current density prepared by embodiment 3
Ring service life and coulombic efficiency figure.
Fig. 8 is bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries following under the different scanning period prepared by embodiment 4
Ring volt-ampere test chart.
Specific embodiment
Technical solution of the present invention is further illustrated with specific embodiment below, but the invention is not limited to embodiments.
Embodiment 1
(1) 1mmol bismuth nitrate is taken to be dissolved in 20ml glycerine, magnetic agitation obtains the nothing of 0.05mol/L to being completely dissolved
The transparent bismuth nitrate solution of color, and the polyvinyl alcohol 400 that 1ml is added is uniformly mixed.
(2) 1mmol sodium fluoride is taken to be dissolved in the Fluorinse for being configured to 0.01mol/L in 20ml deionized water.It will fluorination
Sodium solution is added drop-wise in bismuth nitrate solution, stirs 1h at room temperature, obtains white precipitate.Will precipitating respectively with deionized water, anhydrous
Ethyl alcohol is successively washed repeatedly and is separated by solid-liquid separation, and obtained solids is dried in vacuo to 18h at 80 DEG C and prepares fluorine oxidation
Bismuth material.
(3) bismuth oxyfluoride material prepared by embodiment 1 is carried out using JEOLJEM-3010 type scanning electron microscope
Test, as shown in Figure 1, cluster-shaped structure is presented in the bismuth oxyfluoride material, microspherulite diameter is about 1.5 μm.
Spherical nickel hydroxide material is tested using JEOLJEM-3010 type scanning electron microscope, as shown in Fig. 2,
The nickel hydroxide material is microballoon pattern, micron bulb diameter is about 5~15 μm.
Test analysis shows that the ball-shape nickel hydroxide crystal form is beta crystal type；Element quality percentage is pressed in nickel hydroxide material
Than be calculated as nickel 54.63%, cobalt 4.25%, zinc 3.34%, cobalt hydroxide 5.00%, remaining be the nonmetalloids such as hydrogen, oxygen；Material
Apparent density be 1.69g/cm3, tap density 2.26g/cm3, specific surface area 12.01m2/ g, middle partial size are 10.48 μm.
(4) the bismuth oxyfluoride material 80% that obtains according to embodiment 1, conductive agent 10%, binder 10% quality percentage
It is more spare than weighing, binder PVDF is dissolved with suitable n-methyl-2-pyrrolidone first, then sequentially adds conductive agent acetylene
Black, bismuth oxyfluoride material is tuned into paste and is applied in nickel foam, 100 DEG C of drying 12h, and bismuth oxyfluoride electricity is obtained after roll-in and cutting
Pole piece.
According to nickel hydroxide material 80%, conductive agent 10%, binder 10% mass percent weigh it is spare, then according to
It is secondary that PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material are uniformly mixed and are tuned into paste and are applied in nickel foam,
Nickel hydroxide electrode piece is obtained after 100 DEG C of drying 12h, roll-in and cutting.
(5) nickel hydroxide electrode piece/diaphragm/bismuth oxyfluoride electrode slice is sequentially placed into special battery mould and is configured to
The sandwich structure of two electrodes, then the KOH electrolyte of 6mol/L is added dropwise and is assembled into fluorine then by battery mould fit sealing
Bismuth oxide/nickel hydroxide secondary alkaline batteries.
(6) using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, to prepared bismuth oxyfluoride/hydrogen-oxygen
Change nickel secondary alkaline batteries and carry out constant current charge-discharge test at room temperature, the voltage window of battery is 0.4~1.3V.Such as Fig. 5 institute
Show, the voltage platform of discharge curve is 0.6~0.85V, battery specific capacity under the current density of 0.5A/g be 227mAh/g,
Specific capacity 189.5mAh/g, the specific capacity 162.9mAh/g when current density is 2A/g when current density is 1A/g.
Embodiment 2
(1) 1mmol bismuth nitrate is taken to be dissolved in 20ml ethylene glycol, magnetic agitation obtains the nothing of 0.05mol/L to being completely dissolved
The transparent bismuth nitrate solution of color.
(2) 5.35mmol potassium fluoride is taken to be dissolved in the potassium fluoride solution for being configured to 0.107mol/L in 50ml deionized water.It will
Potassium fluoride solution is added in bismuth nitrate solution, is stirred 3h under ice-water bath, is obtained white precipitate.Precipitating is used into deionization respectively
Water, dehydrated alcohol successively wash repeatedly, and are separated by solid-liquid separation, and by obtained solids, dry 12h prepares fluorine at 130 DEG C
Bismuth oxide material.
(3) bismuth oxyfluoride material prepared by embodiment 2 is tested using XRD-6000 type x-ray diffractometer, such as
Shown in Fig. 3, sample is in 2 θ=14.2 °, and 27.7 °, 28.6 °, 33.7 °, 37.5 °, 43.5 °, 44.8 °, 48.5 °, 50.2 ° are waited positions
Have that obvious characteristic peak is consistent with standard card (JCPDS No.73-1595), corresponding to crystal face be respectively 001,
101、002、110、102、003、112、200、103。
(4) with (4) in embodiment 1
(5) nickel hydroxide electrode piece/diaphragm/bismuth oxyfluoride electrode slice is sequentially placed into special battery mould and is configured to
The sandwich structure of two electrodes, then the mixed electrolytic solution of the KF of KOH and 1mol/L that concentration is 6mol/L is added dropwise, then by battery
Mold fit sealing is assembled into the bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries.
(6) using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, to prepared bismuth oxyfluoride/hydrogen-oxygen
Change nickel secondary alkaline batteries and carries out cyclic voltammetry at room temperature.Fig. 6 is prepared bismuth oxyfluoride electrode in different scanning speed
The cyclic voltammetry curve of (5,10,20,50mV/s) under rate, as can be seen from the figure apparent redox peaks, reduction peak have two
A, peak position at 0.6V and 0.9V, aoxidizes peak position at 1.1V respectively.And increase with sweep speed, cyclic voltammetry curve is
Deformation, reduction peak peak position are basically unchanged under low sweep speed, are increased with sweep speed to low potential movement under high sweep speed；
Oxidation peak peak position increases mobile to high potential with sweep speed.
Embodiment 3
(1) it takes 9mmol bismuth oxide to be dissolved in appropriate nitric acid, is configured to the solution that bismuth concentration is 0.1mol/L, and add
Enter 1ml OP-10 emulsifier；Hydrofluoric acid is configured to the solution of 0.1mol/L；Above-mentioned hydrofluoric acid solution is added to bismuth solution
In, 5h is stirred at room temperature, obtains white precipitate.Precipitating is successively washed with deionized water, dehydrated alcohol respectively and carries out solid-liquid
Separation, by obtained solids, dry 12h prepares bismuth oxyfluoride material at 120 DEG C.
(2) using 3020 type specific surface area of TriStar II and pore-size distribution instrument to bismuth oxyfluoride prepared by embodiment 3
Material is tested, and learns that the specific surface area of the bismuth oxyfluoride material is 45m2/g.From fig. 4, it can be seen that the nitrogen of material prepared is inhaled
Desorption isotherm is typical IVth class adsorption isotherm, illustrates it with meso-hole structure.It, should according to the classification of mesoporous hysteresis loop
Hysteresis loop belongs to H3 type hysteresis loop, it is believed that is that the slit pore formed is accumulated by platy particle.
(3) the bismuth oxyfluoride material 75% that obtains according to embodiment 3, conductive agent 15%, binder 10% quality percentage
It is more spare than weighing, binder PVDF is dissolved with suitable n-methyl-2-pyrrolidone first, then sequentially adds conductive agent acetylene
Black, bismuth oxyfluoride material is tuned into paste and is applied in nickel foam, 110 DEG C of drying 12h, and bismuth oxyfluoride electricity is obtained after roll-in and cutting
Pole piece.
According to nickel hydroxide material 85%, conductive agent 10%, binder 5% mass percent weigh it is spare, then according to
It is secondary that PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material are uniformly mixed and are tuned into paste and are applied in nickel foam,
Nickel hydroxide electrode piece is obtained after 110 DEG C of drying 12h, roll-in and cutting.
(4) nickel hydroxide electrode piece/diaphragm/bismuth oxyfluoride electrode slice is sequentially placed into special battery mould and is configured to
The sandwich structure of two electrodes, then the NH of the KOH and 1mol/L of 6mol/L is added dropwise4Then F electrolyte fastens battery mould close
Envelope is assembled into the bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries.
(5) using the BTS-3000 cell tester of the new Weir Electronics Co., Ltd. production in Shenzhen, the voltage window of battery
Mouth is 0.4~1.3V, carries out cycle life survey at room temperature to prepared bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries
Examination.As shown in fig. 7, battery after 500 constant current charge-discharges recycle, still keeps initial specific volume under the current density of 2A/g
87% or more of amount, coulombic efficiency is maintained in 95%~100%, illustrates that the battery has good cyclical stability, reversible
Property.
Embodiment 4
(1) it takes 10mmol bismuth nitrate and 0.2g acetylene black to be mixed in 10ml ethylene glycol, is configured to bismuth ion and acetylene black
Mix suspending solution system.
(2) 10mmol ammonium fluoride is taken to be dissolved in the ammonium fluoride solution for being configured to 0.1mol/L in 100ml deionized water.It will fluorination
Ammonium salt solution is added in the system of step (1), is stirred 4h at room temperature, is largely precipitated, and reaction system is in grey black at this time.It will
Precipitating is successively washed repeatedly respectively and is separated by solid-liquid separation with deionized water and dehydrated alcohol, by obtained solids in 120 DEG C
Lower vacuum drying 10h prepares bismuth oxyfluoride/acetylene black composite material.
(3) the quality percentage of the bismuth oxyfluoride/acetylene black composite material 90%, binder 10% that obtain according to embodiment 4
It is more spare than weighing, binder PVDF is dissolved with suitable n-methyl-2-pyrrolidone first, bismuth oxyfluoride/acetylene is then added
Black composite material is tuned into paste and is applied in nickel foam, 110 DEG C of drying 12h, obtains bismuth oxyfluoride electrode slice after roll-in and cutting.
According to nickel hydroxide material 85%, conductive agent 10%, binder 5% mass percent weigh it is spare, then according to
It is secondary that PTEF emulsion binder, conductive agent acetylene black, nickel hydroxide material are uniformly mixed and are tuned into paste and are applied in nickel foam,
Nickel hydroxide electrode piece is obtained after 110 DEG C of drying 12h, roll-in and cutting.
(4) nickel hydroxide electrode piece/diaphragm/bismuth oxyfluoride electrode slice is sequentially placed into special battery mould and is configured to
The sandwich structure of two electrodes, then the NaF electrolyte of the KOH and 0.5mol/L of 6mol/L is added dropwise, then battery mould is fastened
Sealing is assembled into the bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries.
(5) using the CHI660A electrochemical workstation of Shanghai Chen Hua company production, to the bismuth oxyfluoride/hydrogen-oxygen constructed
Change nickel secondary alkaline batteries and carry out cyclic voltammetry at room temperature, the voltage window of battery is 0.4~1.3V, and sweep speed is
5mV/s.As shown in figure 8, prepared nickel bismuth secondary cell under the different scanning period (first, ten, 20 time) cyclic voltammetric
Curve, oxidation peak peak position are 1.2V, and reduction peak peak position is 0.66V and 0.93V, as seen from the figure the oxygen under different cycle periods
Change peak and reduction peak peak position be basically unchanged, cyclic voltammetry curve favorable reproducibility, this shows that the battery has outstanding circulating and reversible
Stability.
Claims (8)
1. a kind of bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries, it is characterised in that: using bismuth oxyfluoride material as the cathode of battery
Active material, using nickel hydroxide material as the positive electrode active materials of battery, using aqueous slkali as electrolyte solution, the voltage window of battery
Mouth is 0.4 ~ 1.3V；
In the nickel hydroxide material mass percent of contained element be nickel 48 ~ 63%, cobalt 0.5 ~ 12%, zinc 0.5 ~ 6.5%,
Cerium 0 ~ 8.5%, remaining be hydrogen, oxygen nonmetalloid；The specific surface area of nickel hydroxide material is 5 ~ 100m2/ g, partial size are 1 ~ 15 μ
M, the apparent density of material is 1.58 ~ 1.75g/cm3, material tap density be 2.0 ~ 2.5g/cm3；
For the bismuth oxyfluoride material by constituting with a thickness of the nanometer sheet of 3 ~ 30nm, specific surface area is 10 ~ 500m2/g；It is prepared
Method includes the following steps:
(1) soluble bismuth raw material is dissolved in solvent, is configured to the bismuth ion solution that concentration is 0.01 ~ 5mol/L；
Alternatively, insoluble bismuth raw material is dissolved in acid, it is configured to the bismuth ion solution that concentration is 0.01 ~ 5mol/L；
Alternatively, the bismuth raw material that solubility product constant is greater than bismuth oxyfluoride solubility product constant is added in solvent, it is solid to be configured to bismuth raw material
Content is the solid-liquid mixtures of 5 ~ 200g/L；
Alternatively, a certain amount of regulator is added in above-mentioned bismuth-containing solution again, the addition quality of regulator is bismuth raw material quality
0.1%~50%；
Alternatively, a certain amount of carbon materials are added in above-mentioned bismuth-containing solution again, the addition quality of carbon materials is bismuth raw material matter
The 1% ~ 10% of amount；
(2) it is (1:0.9) ~ (0.9:1) by the molar ratio of bismuth and fluorine, fluoride solution is added drop-wise to the bismuth-containing solution of step (1)
In, 0 DEG C ~ 60 DEG C at a temperature of reacted using stirring or ultrasound, react and precipitating is used into deionization respectively after 0.5 ~ 10h
Water, dehydrated alcohol are successively washed repeatedly and are separated by solid-liquid separation, and obtained solids is dried 6 ~ 36h at 60 DEG C ~ 150 DEG C
Prepare bismuth oxyfluoride material.
2. bismuth oxyfluoride according to claim 1/nickel hydroxide secondary alkaline batteries, which is characterized in that the bismuth is former
Material includes bismuth metal, bismuth oxide, bismuth hydroxide, waltherite, basic bismuth carbonate, sulfuric acid oxygen bismuth, novismuth, bismuth sulfate, nitric acid
One or more of bismuth, halogenation bismuth, bismuth acetate；
The regulator is dodecyl sodium sulfate, polyvinyl pyrrolidone, OP-10 emulsifier, sodium citrate, salicylic acid
One or more of sodium, sodium tartrate, cetyl trimethylbenzene ammonium bromide, polyvinyl alcohol；
The carbon materials are one or more of acetylene black, activated carbon, graphitized carbon, graphene.
3. bismuth oxyfluoride according to claim 1/nickel hydroxide secondary alkaline batteries, which is characterized in that the solvent,
Including water, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, ethylene glycol, glycerine, triethanolamine, polyethylene glycol, diethylene glycol (DEG), three
One or more of glycol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether.
4. bismuth oxyfluoride according to claim 1/nickel hydroxide secondary alkaline batteries, which is characterized in that the acid is
One or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, benzoic acid, phenylacetic acid, dodecyl benzene sulfonic acid.
5. bismuth oxyfluoride according to claim 1/nickel hydroxide secondary alkaline batteries, which is characterized in that the fluorination
One or more of object, including hydrofluoric acid, ammonium fluoride, sodium fluoride, sodium bifluoride, potassium fluoride, potassium hydrogen fluoride.
6. bismuth oxyfluoride described in any one of claim 1 to 5/nickel hydroxide secondary alkaline batteries preparation method, feature
It is, includes the following steps:
(a) preparation of bismuth oxyfluoride electrode and nickel hydroxide electrode
Bismuth oxyfluoride electrode: claim by the mass percent of bismuth oxyfluoride material 70 ~ 95%, conductive agent 3 ~ 15%, binder 2 ~ 15%
Binder, is dissolved in n-methyl-2-pyrrolidone by amount first, is made into the solution of 0.01 ~ 0.04 g/ml, then by bismuth oxyfluoride
Material, conductive agent are added in binder solution, are evenly stirred until paste, are coated on a current collector, then by it at 80 ~ 150 DEG C
Drying box in dry 5 ~ 36h, electrode slice is cut into after roll-in to get to bismuth oxyfluoride electrode slice；
Nickel hydroxide electrode: claim according to the mass percent of nickel hydroxide material 70 ~ 95%, conductive agent 3 ~ 15%, binder 2 ~ 15%
It measures spare, then successively binder, conductive agent, nickel hydroxide material is uniformly mixed and is tuned into paste and is applied in nickel foam, 80 ~
Nickel hydroxide electrode piece is obtained after 150 DEG C of dry 5 ~ 36h, roll-in and cutting；
(b) bismuth oxyfluoride/nickel hydroxide secondary alkaline batteries preparation
Nickel hydroxide electrode piece, diaphragm, bismuth oxyfluoride electrode slice are sequentially placed into Sanming City that two electrodes are configured in battery mould
It controls structure, is added dropwise mold fit sealing after alkaline aqueous electrolyte.
7. bismuth oxyfluoride according to claim 6/nickel hydroxide secondary alkaline batteries preparation method, which is characterized in that
The binder is one or both of Kynoar, ptfe emulsion, sodium carboxymethylcellulose, butadiene-styrene rubber
More than；The conductive agent is one or more of acetylene black, carbon black, graphite, graphene；The collector is more
Hole is netted, foil-like or textile-like high electronic conductivity material, is related to nickel foam, nickel foil or nickel screen, copper mesh or copper foil, stainless
Steel mesh, stainless 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 of.
8. bismuth oxyfluoride according to claim 6/nickel hydroxide secondary alkaline batteries preparation method, which is characterized in that
The diaphragm is to be grafted poly- third poly- non-woven fabrics, graft PP microporous barrier, all-glass paper, nylon nonwoven fabrics, polyvinyl alcohol film, stone
One or more of cotton paper；The electrolyte is one or two or more kinds of alkali metal hydroxides, concentration 1
~8.0mol/L；It also include the assisted electrolysis of one or more of potassium fluoride, sodium fluoride or ammonium fluoride in electrolyte
Matter, the concentration of assisted electrolysis matter are 0.05 ~ 6mol/L.
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| CN108281642B (en) * | 2018-01-17 | 2020-05-05 | 南京信息工程大学 | Flower-shaped structure BiOBr electrode material, preparation method and electrochemical energy storage application thereof |
| CN108483494B (en) * | 2018-02-27 | 2021-02-09 | 南京信息工程大学 | Nano flaky BiOI and application thereof as electrode material |
| CN108467062A (en) * | 2018-02-27 | 2018-08-31 | 南京信息工程大学 | A kind of rose-shaped BiOCl and the purposes as electrode material |
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