CN106684362B - A kind of zinc-nickel battery anode material - Google Patents
A kind of zinc-nickel battery anode material Download PDFInfo
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- CN106684362B CN106684362B CN201710043929.6A CN201710043929A CN106684362B CN 106684362 B CN106684362 B CN 106684362B CN 201710043929 A CN201710043929 A CN 201710043929A CN 106684362 B CN106684362 B CN 106684362B
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- zinc
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- carbonate
- nickel battery
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
Abstract
The invention discloses a kind of zinc-nickel battery anode material, for the present invention using basic zinc carbonate/carbon composite as cathode active material of zinc-nickel battery, preparation is built into Soft Roll NiZn battery containing basic zinc carbonate/carbon composite Zinc-nickel battery negative and Ni anode.Test result shows: the material is as cell negative electrode material in use, improving the whole chemical property of the electrode comprising the material and battery.Soft-package battery obtained has high energy density, the cycle life of coulombic efficiency and length.
Description
Technical field
The invention belongs to technical field of energy storage, in particular to a kind of zinc-nickel battery anode material.
Background technique
Zinc-nickel secondary batteries have high-energy density, high power density, high working voltage, wide operating temperature, memoryless effect
The features such as answering is a kind of environmentally protective high-performance secondary cell.But cathode generates deformation and zinc in charge and discharge process
The problems such as dendritic growth, shortens battery, constrains the development of zinc-nickel secondary batteries.
Traditional Zinc-nickel battery negative preparation is that ZnO, zinc powder, conductive agent and binder are modulated into slurry, and slurry is applied
Cream is pressed into electrode on foam copper or copper grid.During the charging process, zinc dendrite is generated.The growth of zinc dendrite is so that active material
Falling off from electrode causes battery cycle life to reduce, or penetrates the damage that diaphragm causes the short circuit of positive and negative interpolar to cause battery.
In charge and discharge process, active material can redistribute zinc electrode in electrode surface simultaneously, the activity at zinc electrode top and edge
Substance is gradually decreased or is disappeared, and electrode base causes the deformation of zinc electrode with intermediate progressive additive.The result of deformation makes electrode ratio
Surface area reduces, and real work current density increases, and overpotential increases, and causes to aoxidize utilization rate of zinc decline, zinc electrode capacity drop
Low, the zinc-nickel cell service life reduces.
Patent CN104993106A discloses a kind of preparation method and application of Zinc-base compounded material basic zinc carbonate, system
Standby material is obtained using zinc acetate, sodium fluoride and hexamethylenetetramine by hydro-thermal reaction, it is believed that is had in terms of lithium ion battery
Potential application, but the charging and discharging curve figure of its battery provided show its discharge platform in 0.6V, and the electric discharge of lithium ion battery
Platform is in 3.2~3.7V, and basic zinc carbonate can not carry out the insertion of lithium ion and take off without the layer structure of similar graphite
It is embedding, therefore basic zinc carbonate is not suitable for the negative electrode material as lithium ion battery.
Summary of the invention
Object of the present invention is to overcome oxidation utilization rate of zinc decline in the prior art, the reduction of zinc electrode capacity, zinc-nickel cell longevity
The problem of life reduces, provides that a kind of preparation process is simple, a kind of system of the mild novel zinc-nickel battery anode material of reaction condition
Preparation Method.
The technical scheme is that make a kind of method of its surface growth basic zinc carbonate using the carbon material of modified,
Basic zinc carbonate is combined together by chemical bond and carbon material, and the presence of chemical bond can be realized electronics fast transferring；It obtains
Basic zinc carbonate/carbon composite with excellent conductive performance and calcium hydroxide, bismuth oxide and PTFE in certain proportion
Be modulated into homogeneous slurry coated on brass screen or three-dimensional tin-coated copper on the net together it is repressed, dry, be cut into electrode, with it and make
Material for anode is assembled into soft-package battery, has good electric property.
According to the first object of the present invention, the present invention provides a kind of zinc-nickel battery anode material, the zinc-nickel cells
Negative electrode material is modulated into equal chylema by basic zinc carbonate/carbon composite, calcium hydroxide, bismuth oxide and PTFE in certain proportion
Material, the basic zinc carbonate/carbon composite, which is reacted by urea or ammonium hydrogen carbonate with zinc salt and carbon material, to be made；
The carbon material is carbon nanotube, carbon fiber, conductive black or graphene etc..
In the zinc-nickel battery anode material, count by weight percentage, zinc carbonate/carbon composite: calcium hydroxide: oxygen
Change bismuth: PTFE=92:1:3:4, wherein PTFE is selected from the 0.1%wt water slurry that commercially available 60%wt product is diluted to, PTFE
Ratio used is calculated according to pure PTFE.
Above-mentioned carbon material is the carbon material that surface has oxygen-containing group modification.
Basic zinc carbonate/the carbon composite, which is reacted by urea with zinc salt and carbon material, to be made, specific preparation method packet
Include following steps:
1) mixed liquor that the zinc salt solution that compound concentration is 0.3~1.0mol/L is mixed with carbon material；
2) compound concentration is the aqueous solution of urea of 3.0~15mol/L；
3) step 1) mixed liquor is uniformly mixed with aqueous solution of urea, heating reaction；Filter after reaction, spend from
Sub- water washing to neutral, drying obtains basic zinc carbonate/carbon composite of black.
Specifically, above-mentioned steps 1) in zinc salt can be ZnCl2、Zn(NO3)2、ZnSO4Deng zinc member in carbon material and zinc salt
Plain mass ratio is 1:3~6.
Specifically, above-mentioned steps 3) in zinc salt and urea mol ratio be 1:3~4, preferably 1:3,1:3.5 or 1:4；Reaction
Temperature is 90 DEG C, reaction time 12h.
Basic zinc carbonate/the carbon composite, which is reacted by ammonium hydrogen carbonate with zinc salt and carbon material, to be made, specific preparation side
Method includes the following steps:
1) mixed liquor that the zinc salt solution that compound concentration is 0.3~1.0mol/L is mixed with carbon material；
2) compound concentration is the ammonium bicarbonate aqueous solution of 1.5~3.0mol/L；
3) prepared ammonium bicarbonate aqueous solution is slowly added dropwise into step 1) mixed liquor, is stirred to react；Reaction terminates
It filters afterwards, be washed with deionized to neutral, drying and obtain basic zinc carbonate/carbon composite of black.
Specifically, above-mentioned steps 1) in zinc salt can be ZnCl2、Zn(NO3)2、ZnSO4Deng zinc member in carbon material and zinc salt
Plain mass ratio is 1:3~6.
Specifically, above-mentioned steps 3) in zinc salt and ammonium hydrogen carbonate molar ratio be 1:2.2~2.5.
Specifically, above-mentioned steps 3) in reaction temperature be 60 DEG C, the reaction was continued 2h after ammonium bicarbonate aqueous solution is added dropwise.
A kind of zinc-nickel cell using above-mentioned zinc-nickel battery anode material, the energy density of the battery are
140Wh·kg-1, when, cyclical stability is not less than 1000 times.
The present invention, which is grown using basic zinc carbonate in carbon material surface, obtains basic zinc carbonate/carbon composite, then uses
Composite material replaces tradition ZnO as active material and prepares cathode；It is assembled into Soft Roll NiZn battery with anode, in the composite
Basic zinc carbonate is combined together by chemical bond and carbon material, and the presence of chemical bond can be realized electronics fast transferring, is reduced
The network structure of the internal resistance of cathode, carbon material composition also improves the utilization rate of active material, and the battery of assembling shows excellent
Different chemical property.
The beneficial effects of the present invention are: (1) it is of the invention reaction condition it is mild, raw material sources used extensively, cost
Cheap, stable process conditions are reliable, and entire process flow is simple and easy, are suitable for industrialized production；(2) present invention uses alkali formula
Zinc carbonate/carbon composite replaces active material and additive calcium hydroxide of traditional zinc oxide as Zinc-nickel battery negative
Homogeneous slurry is modulated into certain proportion with bismuth oxide as negative electrode material, when being assembled into soft-package battery with positive electrode,
Energy density and power density with higher, while when energy density is in 140Whkg-1, cyclical stability is not less than 1000
It is secondary.
Detailed description of the invention
Fig. 1 is basic zinc carbonate/carbon composite electron microscope of urea preparation；
Fig. 2 is basic zinc carbonate/carbon composite electron microscope of ammonium hydrogen carbonate preparation；
Fig. 3 is basic zinc carbonate/carbon composite XRD diagram of urea preparation；
Fig. 4 is basic zinc carbonate/carbon composite XRD diagram of ammonium hydrogen carbonate preparation；
Charging and discharging curve when Fig. 5 is products therefrom of the present invention and positive electrode composition NiZn battery；
(charging current is stable circulation figure when Fig. 6 is products therefrom of the present invention and positive electrode composition NiZn battery
20mA, discharge current 20mA)
Fig. 7 is energy density of the obtained NiZn battery of negative electrode material under different electric currents obtained by the present invention.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the invention.
Carbon material used in embodiment be surface have oxygen-containing group modification carbon material, specific preparation method referring to
The introduction of the preparation method of carbon material surface functionalization is completed in embodiment 4 in 105449194 A of CN.
Basic zinc carbonate/carbon composite prepared by embodiment 1, urea
100mg carbon material (carbon nanotube, carbon fiber, conductive black or graphene) is weighed, is added in 50mL water ultrasonic
1g divalent zinc salt (ZnCl is added thereto after dispersion 30min2) stir and continue ultrasonic disperse 10min after completely dissolution；Weigh one
Quantitative urea (1.32g, 1.50g or 1.77g) is dissolved in 30mL water；Two above solution is uniformly mixed, addition is stirred
Sub- sealing is mixed, sustained response 12h under magnetic stirring is placed it in 90 DEG C of oil bath pan.Filter after reaction, spend from
Basic zinc carbonate/carbon composite can be obtained in sub- water washing to neutral, 50 DEG C of drying.
The basic zinc carbonate of preparation/carbon composite electron microscope and XRD diagram are as shown in attached drawing 1 and attached drawing 3.
Basic zinc carbonate/carbon composite prepared by embodiment 2, ammonium hydrogen carbonate
100mg carbon material (carbon nanotube, carbon fiber, conductive black or graphene) is weighed, is added in 50mL water ultrasonic
1g ZnSO is added thereto after dispersion 30min4Stirring continues ultrasonic disperse 10min after completely dissolution；Weigh a certain amount of bicarbonate
Ammonium (0.92,1.0g or 1.05g) plus 15mL water sufficiently dissolve；Mixing liquor is placed in 60 DEG C of oil bath pan, while magnetic
Power stirring, prepared ammonium bicarbonate soln is slowly added dropwise into mixed solution.The reaction was continued after dripping two hours,
It filters after reaction, be washed with deionized to neutral, 50 DEG C of drying basic zinc carbonate/carbon composite can be obtained.
The basic zinc carbonate of preparation/carbon composite electron microscope and XRD diagram are as shown in attached drawing 2 and attached drawing 4.
The cathode piece preparation method of embodiment 3, basic zinc carbonate/carbon composite as active material
Basic zinc carbonate/carbon composite, calcium hydroxide, bismuth oxide, binder PTFE (suspension of 0.1%wt water) are pressed
The ratio mixing of 92:1:3:4 is tuned into paste, it tabletting, is cut coated on brass screen or three-dimensional tin plating copper mesh, drying
To negative electrode tab.
Embodiment 4, Soft Roll NiZn battery assembly
By folder among the zinc load piece of preparation, nickel positive plate across by having modified polypropene felt and wettable polyolefin hole
Composite diaphragm made of film is bonded, KOH that implantation quality concentration is 30% (zinc oxide is saturation), mass concentration are 2%
The electrolyte for the Sodium Polyacrylate that LiOH and mass concentration are 6%, finally Soft Roll zinc-nickel cell is made in sealing.
Battery performance test:
1. the zinc-nickel cell of embodiment preparation is discharged to voltage for 0.8V, according to electric discharge with 20mA charging 7min, 20mA
Curve and discharge capacity find its mid-point voltage that discharges.The energy density (see Fig. 5) of battery is calculated, while measuring following for battery
Ring stability (see Fig. 6).
2. the zinc-nickel cell of embodiment preparation is carried out to the measurement of battery capacity with different charging currents and discharge current,
Discharge cut-off voltage is 0.8V, and test result is shown in Fig. 7, it can be seen that when charge and discharge electric current is 10mAcm-2, 20mAcm-2,
40mA·cm-2, 80mAcm-2, the specific capacity of battery is respectively 159mAhg-1, 154mAhg-1, 135mAhg-1,
109mAh·g-1。
It can be seen that using basic zinc carbonate/carbon composite from the above test result as main active substances preparation
Electrode can effectively improve the energy density and cycle life of battery, this should be attributed to when using basic zinc carbonate/carbon
When composite material prepares electrode, since the oxygen in oxygen-containing group has lone electron pair, Zn2+With unoccupied orbital, therefore composite material
Coordinative Chemistry key is formed between middle active material and carbon material, be conducive in charge and discharge process electronics can fast transfer, subtract
The internal resistance of few electrode, so as to improve the comprehensive performance of battery.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from of the invention
In the case where spirit and scope, embodiments of the present invention can be made with various changes, replacement and change.
Claims (9)
1. a kind of zinc-nickel battery anode material, the zinc-nickel battery anode material is by basic zinc carbonate/carbon composite, hydroxide
Calcium, bismuth oxide and polytetrafluoroethylene (PTFE) composition, the basic zinc carbonate/carbon composite is by urea or ammonium hydrogen carbonate and zinc salt and carbon
Material reaction is made, and the carbon material is the carbon material that surface has oxygen-containing group modification.
2. zinc-nickel battery anode material according to claim 1, it is characterised in that: the carbon material is carbon nanotube, carbon fiber
Dimension, conductive black or graphene.
3. zinc-nickel battery anode material according to claim 1, it is characterised in that: count by weight percentage, basic carbonate
Zinc/carbon composite: calcium hydroxide: bismuth oxide: polytetrafluoroethylene (PTFE)=92:1:3:4.
4. any one of -3 zinc-nickel battery anode material according to claim 1, it is characterised in that: the basic zinc carbonate/carbon
Composite material, which is reacted by urea with zinc salt and carbon material, to be made, and specific preparation method includes the following steps:
1) mixed liquor that the zinc salt solution that compound concentration is 0.3~1.0mol/L is mixed with carbon material；
2) compound concentration is the aqueous solution of urea of 3.0~15mol/L；
3) step 1) mixed liquor is uniformly mixed with aqueous solution of urea, heating reaction；It filters after reaction, use deionized water
Washing to neutral, drying obtains basic zinc carbonate/carbon composite of black.
5. zinc-nickel battery anode material according to claim 4, it is characterised in that: the zinc salt in step 1) is ZnCl2、Zn
(NO3)2、ZnSO4Or it corresponds to hydrate, the mass ratio of Zn-ef ficiency is 1:3~6 in carbon material and zinc salt.
6. zinc-nickel battery anode material according to claim 4, it is characterised in that: the molar ratio of zinc salt and urea in step 3)
For 1:3~4；The reaction temperature is 90 DEG C, reaction time 12h.
7. any one of -3 zinc-nickel battery anode material according to claim 1, it is characterised in that: the basic zinc carbonate/carbon
Composite material, which is reacted by ammonium hydrogen carbonate with zinc salt and carbon material, to be made, and specific preparation method includes the following steps:
1) mixed liquor that the zinc salt solution that compound concentration is 0.3~1.0mol/L is mixed with carbon material；
2) compound concentration is the ammonium bicarbonate aqueous solution of 1.5~3.0mol/L；
3) prepared ammonium bicarbonate aqueous solution is slowly added dropwise into step 1) mixed liquor, is stirred to react；It crosses after reaction
It filters, be washed with deionized to neutral, drying and obtain basic zinc carbonate/carbon composite of black.
8. zinc-nickel battery anode material according to claim 7, it is characterised in that: the zinc salt in step 1) is ZnCl2、Zn
(NO3)2Or ZnSO4, the mass ratio of Zn-ef ficiency is 1:3~6 in carbon material and zinc salt.
9. zinc-nickel battery anode material according to claim 7, it is characterised in that: zinc salt and ammonium hydrogen carbonate rubs in step 3)
You are than being 1:2.2~2.5；Reaction temperature is 60 DEG C, the reaction was continued 2h after ammonium bicarbonate aqueous solution is added dropwise.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993106A (en) * | 2015-05-27 | 2015-10-21 | 三峡大学 | Zinc-based composite material basic zinc carbonate, preparation method and application thereof |
| CN105161702A (en) * | 2015-10-26 | 2015-12-16 | 新乡市超力新能源有限公司 | Zinc-nickel battery negative electrode active substance, zinc-nickel battery negative electrode plate and zinc-nickel battery |
| CN105449194A (en) * | 2015-12-21 | 2016-03-30 | 江苏理工学院 | Cathode material for nickel-zinc battery and nickel-zinc battery employing cathode material |
| CN106025251A (en) * | 2016-07-28 | 2016-10-12 | 新乡市超力新能源有限公司 | Preparation method of negative electrode material of zinc and nickel battery and slurry mixing method of negative electrode of zinc and nickel battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993106A (en) * | 2015-05-27 | 2015-10-21 | 三峡大学 | Zinc-based composite material basic zinc carbonate, preparation method and application thereof |
| CN105161702A (en) * | 2015-10-26 | 2015-12-16 | 新乡市超力新能源有限公司 | Zinc-nickel battery negative electrode active substance, zinc-nickel battery negative electrode plate and zinc-nickel battery |
| CN105449194A (en) * | 2015-12-21 | 2016-03-30 | 江苏理工学院 | Cathode material for nickel-zinc battery and nickel-zinc battery employing cathode material |
| CN106025251A (en) * | 2016-07-28 | 2016-10-12 | 新乡市超力新能源有限公司 | Preparation method of negative electrode material of zinc and nickel battery and slurry mixing method of negative electrode of zinc and nickel battery |
Non-Patent Citations (2)
| Title |
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| "氧化石墨烯与氧化锌复合材料的制备及室温NOx气敏性能研究";柴丽雅等;《人工晶体学报》;20130815;第42卷(第8期);第1611-1615页 * |
| "锌镍电池新进展";陈衍珍;《电源技术》;20000420;第24卷(第2期);第120-123页 * |
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