CN109962242A - A kind of additive of zinc-base battery - Google Patents
A kind of additive of zinc-base battery Download PDFInfo
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- CN109962242A CN109962242A CN201910297877.4A CN201910297877A CN109962242A CN 109962242 A CN109962242 A CN 109962242A CN 201910297877 A CN201910297877 A CN 201910297877A CN 109962242 A CN109962242 A CN 109962242A
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- zinc
- additive
- gallium
- indium
- metal
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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
- H01M10/26—Selection of materials as electrolytes
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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
- H01M4/624—Electric conductive fillers
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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
- H01M4/624—Electric conductive fillers
- H01M4/626—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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 present invention relates to a kind of additives of zinc-base battery.The additive of the zinc-base battery, which is characterized in that the additive is metal, alloy and its one of oxide or hydroxide or a variety of；The metal is one of gallium, indium, tin, lead, bismuth or a variety of；The alloy is one of gallium, indium, tin, lead, the binary in bismuth or multicomponent alloy or a variety of；The metal oxide is one of oxide of gallium, indium, tin, lead, bismuth or a variety of；The hydroxide is one of hydroxide of gallium, indium, tin, lead, bismuth or a variety of.After the additive, the cycle life of zinc-base battery is 500 times or more, can stablize charge and discharge under the multiplying power of 0.1~50C.There is additive of the present invention raw material easily to prepare, high zinc dendrite rejection ability；So that battery is shown excellent chemical property and cyclical stability, can be widely applied to the fields such as various portable electronic devices, electric car and aerospace.
Description
Technical field
The invention belongs to technical field of energy material, and in particular to a kind of additive of zinc-base battery.
Background technique
Continuous with electronics technology breaks through and in the world to the energy, environmentally friendly great attention, research and development novel green
Secondary power battery is always one of the hot spot of the great development in science and technology plan in various countries, and the high-energy based on new material and new technology is close
Degree, pollution-free, the green battery new system that can be recycled continues to bring out, and rapidly developing becomes New Generation of Portable electronic product
Support power supply and electric vehicle, the electrical source of power of hybrid electric vehicle.
Current driving force type Battery Market includes lead-acid battery, nickel-cadmium cell, nickel-metal hydride battery and lithium ion battery, but this
All there are some problems in a little battery systems, constrain the further development of these batteries.Lead-acid battery and ickel-cadmium cell are already
Widely applied secondary cell occupies the staple market of motive-power battery, but these two types of battery energy densities are relatively low, commodity
Battery generally can only achieve 30~50Whkg-1, be not suitable for using in the occasion for needing a large amount of storing energies to move again.Plumbic acid
Battery and nickel-cadmium cell contain the serious heavy metal element of environmental pollution, its production and the processing of waste and old product have seriously environment
It influences, as the waste and old product processing of these batteries of battery production business burden, lead-acid battery and nickel-cadmium cell has been strictly required in European Union
It is that can not achieve sustainable development, limited promise.Ni-H cell jumps up and the technologies such as consistency of battery pack difference because of nickel valence
Problem, with LiCoO2For the commercial Li-ion battery higher cost of positive electrode, safety is poor, fuel cell because technology at
Ripe degree and cost, the in the recent period all more difficult main product as power battery.Novel high-performance green secondary power battery at present
Research and development are own through becoming key subjects in the urgent need to address.
Nickel-zinc cell is made of zinc electrode and nickel electrode, has in zinc-silver oxide cell nickel in zinc load high capacity and ickel-cadmium cell concurrently
The superior function of positive long-life is a kind of High-performance green secondary power battery.Ni-MH secondary battery performance characteristics include: work
It is high (being higher than nickel-metal hydride battery and nickel-cadmium cell) to make voltage, and energy density height (generally 2 times of lead-acid battery, the 1.5 of nickel-cadmium cell
Times), power density height (being only second to lithium ion battery), operating temperature is wide (- 20~50 DEG C), memory-less effect, the production of battery
Pollution is not generated to environment with use process, is known as real green battery, the storage of zinc is abundant, cheap.Nickel zinc
Battery oneself become novel high property more cheap and practical after lead-acid battery, ickel-cadmium cell, Ni-H cell and lithium ion battery
It can green power battery.
Existing research shows that the negative electrode material of nickel-zinc cell is to influence the key factor of its chemical property, use at present
Negative electrode material be mainly metallic zinc.Metallic zinc is oxidized into zinc oxide in nickel-zinc cell cyclic process.Due to zinc oxide
Poorly conductive, in charge and discharge process resistance it is larger, especially high power charging-discharging when electrode generate very big polarization, finally
Lead to the uniform poor circulation of current distribution is uneven.Zinc load the problem of there is also dendritic growths in charge and discharge process, zinc branch
Crystalline substance is hard and densification penetrates readily through diaphragm, causes battery short circuit, eventually leads to battery failure.
For zinc load, the problem, the prior art mainly pass through the thickness of increase diaphragm, mention in charge and discharge process
The methods of high diaphragm being folded without breaking ability, the structure for changing zinc load.These methods have the cycle performance for improving nickel-zinc cell
There is certain effect, but without fundamentally solving the problems, such as that zinc load material own material properties are brought, causes nickel zinc electric
The cycle performance in pond is difficult to further increase, and limits the further application development of nickel-zinc cell.
Summary of the invention
The technical problems to be solved by the present invention are: how to improve causes since zinc load electric conductivity is deteriorated and generates dendrite
Nickel-zinc cell chemical property be deteriorated, cycle life decaying, even battery failure the technical issues of.
For above-mentioned technical problem to be solved, the present invention provides a kind of additives of zinc-base battery, can make
Obtaining nickel-zinc cell has many advantages, such as high capacity, high rate capability, excellent cycling performance.
Realize that the technical solution of the object of the invention is as follows:
A kind of additive of zinc-base battery, which is characterized in that the additive is metal, alloy and its oxygen of low melting point
One of compound or hydroxide are a variety of；
The metal has good inhibition Hydrogen Evolution Performance, specially one of gallium, indium, tin, lead, bismuth or a variety of；
The alloy is one of gallium, indium, tin, lead, the binary in bismuth or multicomponent alloy or a variety of；
The metal oxide is one of oxide of gallium, indium, tin, lead, bismuth or a variety of；
The hydroxide is one of hydroxide of gallium, indium, tin, lead, bismuth or a variety of.
The present invention has been surprisingly found that gallium, indium, tin, lead, bismuth metal and its alloy, oxide, hydroxide by a large number of experiments
It is added in zinc-base battery, its chemical property can be significantly improved.After tested, the zinc-base battery of additive of the present invention is added
In 2C charge and discharge, stablizes specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge, after 500 repeated charges
Capacity can keep the 100% of initial capacity.After the additive, in cyclic process, zinc load surface is without apparent zinc
Dendritic growth, zinc deposit to form equally distributed spherical shape, and a diameter of 2 nanometers~50 microns.
The preferred gallium-indium alloy of the alloy, gallium-indium-tin alloy, gallium indium bismuth alloy, gallium indium metal, gallium indium sn-bi alloy.
It is further preferred that the additive is grouped as by the group of following parts by weight: gallium/indium metal/metallic tin 1-
11 parts, 0-1 parts of bismuth metal, 0-1 parts of metallic lead；Wherein gallium, indium metal, metallic tin mass ratio be (0-9): (0-5):
(0-1), and three is not 0 simultaneously.
It is further preferred that the additive is grouped as by the group of following parts by weight: 5-9 parts of gallium, indium metal 1-5
Part, 0-1 parts of metallic tin, 0-1 parts of bismuth metal, 0-1 parts of metallic lead.
It is further preferred that the additive is grouped as by the group of following parts by weight: 7-9 parts of gallium, indium metal 1-2
Part, 1 part of metallic tin, 0-1 parts of bismuth metal.
The state of the additive can be liquid, powder or block etc..
The present invention also provides application of the above-mentioned additive in zinc-base battery.The zinc-base battery is that can fill zinc-nickel, zinc-
One of air, zinc-manganese, silver-zinc battery.Nickel-zinc battery and the zinc-manganese battery of filling is for large-scale energy-accumulating power station, such as
The peak load regulation network of the clean energy resourcies such as wind energy, solar energy, tide energy.
The present invention also provides the application methods of above-mentioned additive: the additive can be placed in the anode of zinc-base battery, cathode,
The position that diaphragm or other electrolyte can contact.
The quality accounting of the negative electrode material of the additive and zinc-base battery is 0.1~20:100.
The invention has the following advantages over the prior art:
(1) raw material sources of the additive of zinc-base battery provided by the invention are extensive, and preparation process includes simple equal
Even mixing can be obtained, and entire process repeatability is high, process is simple, time-consuming few；It prepares raw material to be easily obtained, is suitable for industrialization
Production.
(2) chemical property drop caused by the additive can improve zinc oxide electrode electric conductivity variation, internal resistance increases
Low phenomenon；
Simultaneously because the additive will be slow in charge and discharge process dissolves and be deposited on metallic zinc negative terminal surface, formed micro-
The spherical structure of Nano grade can effectively inhibit the generation of zinc dendrite, avoid because dendritic growth pierces through caused by diaphragm
Battery failure, the too short problem of cycle life.Additive can replace renovation zinc-base battery after failure, extend battery life and arrive
It is more than 1000 circulations.
(3) show that the additive can be such that nickel-zinc cell has excellent performance by test, make it have higher specific capacity,
When rate charge-discharge of the battery with 1C, the specific capacity of resulting materials is greater than 550mAh/g；With showing good cycle performance,
After 500 repeated charges, specific capacity is still higher than 550mAh/g；Feature platform is obvious, has in 1.6V or so and significantly puts
Level platform.
(4) using the nickel-zinc cell of additive of the present invention, energy density with higher, cycle performance is excellent,
Safety (not exploding not on fire), it is environment-protecting and non-poisonous the advantages that, belong to the next generation can charge and discharge battery, can be widely applied to various portable
The fields such as electronic equipment, electric car and aerospace.
Detailed description of the invention
Fig. 1 is scanning electron microscope of the diaphragm of the zinc-nickel cell described in embodiment 1 containing additive after cycle charge-discharge
Scheme SEM.
Fig. 2 is the charging and discharging curve voltage curve of the zinc-nickel cell described in embodiment 1 containing additive.
Fig. 3 is that the zinc-nickel cell described in embodiment 1 containing additive 1200 constant current cycle performances under 4C multiplying power are bent
Line.
Fig. 4 is 1000 constant current cycle performances of the zinc-nickel cell described in embodiment 1 containing additive under 2C multiplying power
Curve.
Specific embodiment
Following specific embodiments should not be construed as limiting the invention for illustrating the present invention.
In embodiment, unless otherwise instructed, technological means used is this field conventional technology.
Embodiment 1:
A kind of additive of zinc-base battery, is made by the steps to obtain:
At room temperature, by gallium 8g, indium metal 2g, metallic tin 1g are added in mortar, grinding stirring 12 hours or so to get
Additive.
The assembling of nickel-zinc cell: gained additive is coated on the diaphragm of nickel-zinc cell, carries out normal nickel-zinc cell
Assembling.
It is as follows to the test method of the chemical property of nickel-zinc cell:
(1), simulated battery is using button CR2032 type system, and wherein cathode is zinc oxide, just extremely nickel hydroxide.
(2), experiment carries out test point to the reversible capacity and cycle performance of electrode material using the method for constant current charge-discharge
Analysis.Charge and discharge system are as follows: voltage range: 1.2-2.0V；Cycle-index is 1-1500 times.
The pattern of the diaphragm of zinc-nickel cell zinc electrode after cycle charge-discharge is characterized, as a result referring to Fig. 1, by picture
Spherical homodisperse structure is presented in susceptible of proof additive, and the size of spheric granules is 10 nanometers~20 microns.
Fig. 2 is the charging and discharging curve voltage curve of the zinc-nickel cell described in embodiment 1 containing additive.It confirms to have bright
Aobvious nickel-zinc cell platform.
Fig. 3 is that the zinc-nickel cell described in embodiment 1 containing additive 1200 constant current cycle performances under 4C multiplying power are bent
Line.
Fig. 4 is 1000 constant current cycle performances of the zinc-nickel cell described in embodiment 1 containing additive under 2C multiplying power
Curve.
As the result is shown: in 2C charge and discharge, stablizing specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge, 500
Capacity can keep the 100% of initial capacity after secondary repeated charge.
Embodiment 2
The present embodiment provides a kind of nickel-zinc cells, and unlike the first embodiment, additive described in embodiment 1 is placed on
Zinc load.
Corresponding electric performance test is carried out, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；
Under above-mentioned multiplying power when charge and discharge, capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 3
The present embodiment provides a kind of nickel-zinc cells, and unlike the first embodiment, additive described in embodiment 1 is placed on
Electrolyte.
Corresponding electric performance test is carried out, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；
Under above-mentioned multiplying power when charge and discharge, capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 4
This example provides a kind of additive, preparation method substantially with embodiment 1, unlike, in additive component
Tin is replaced with bismuth metal；Specifically: at room temperature, gallium 8g, indium metal 2g, bismuth metal 1g are added in mortar, grinding stirring
12 hours or so to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 90% of initial capacity after 500 repeated charges.
Embodiment 5
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
The tin in agent ingredient is added to be replaced with metallic lead；Specifically: at room temperature, mortar is added in gallium 8g, indium metal 2g, metallic lead 1g
In, grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 85% of initial capacity after 500 repeated charges.
Embodiment 6
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
The tin in agent ingredient is added to remove；Specifically: at room temperature, gallium 8g, indium metal 2g are added in mortar, agitation grinding 12 hours
Left and right is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 400mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 80% of initial capacity after 500 repeated charges.
Embodiment 7
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient and indium removal；Specifically: at room temperature, gallium 8g is added in mortar, grinding stirring 12 hours or so,
Up to additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 400mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 60% of initial capacity after 500 repeated charges.
Embodiment 8
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient and gallium removal；Specifically: at room temperature, indium metal 2g is added in mortar, grinding stirring 12 hours or so,
Up to additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 82% of initial capacity after 500 repeated charges.
Embodiment 9
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the gallium in agent ingredient and indium removal；Specifically: at room temperature, metallic tin 1g is added in mortar, grinding stirring 12 hours or so,
Up to additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 400mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 75% of initial capacity after 500 repeated charges.
Embodiment 10
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient to remove, and be to be adjusted to 9:1 the quality of gallium and indium: specifically: at room temperature, by gallium 9g, indium metal
1g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 92% of initial capacity after 500 repeated charges.
Embodiment 11
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient to remove, and is to be adjusted to 7:3 the quality of gallium and indium；Specifically: at room temperature, by gallium 7g, indium metal
3g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 90% of initial capacity after 500 repeated charges.
Embodiment 12
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient to remove, and is to be adjusted to 6:4 the quality of gallium and indium；Specifically: at room temperature, by gallium 6g, indium metal
4g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 85% of initial capacity after 500 repeated charges.
Embodiment 13
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add the tin in agent ingredient to remove, and is to be adjusted to 5:5 the quality of gallium and indium；Specifically: at room temperature, by gallium 5g, indium metal
5g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 500mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 81% of initial capacity after 500 repeated charges.
Embodiment 14
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
The ratio of the gallium in agent ingredient, indium, tin is added to be changed to 9:1:1；Specifically: at room temperature, by gallium 9g, indium metal 1g, metallic tin
1g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 15
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
The ratio of the gallium in agent ingredient, indium, tin is added to be changed to 8:1:1；Specifically: at room temperature, by gallium 8g, indium metal 1g, metallic tin
1g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 16
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
The ratio of the gallium in agent ingredient, indium, tin is added to be changed to 7:2:1；Specifically: at room temperature, by gallium 7g, indium metal 2g, metallic tin
1g is added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 17
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add and bismuth is added in agent ingredient, and makes the ratio 8:2:1:1 of gallium, indium, tin, bismuth；Specifically: at room temperature, by gallium 8g, metal
Indium 2g, metallic tin 1g, bismuth metal 1g are added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 100% of initial capacity after 500 repeated charges.
Embodiment 18
This example provides a kind of additive of zinc-base battery, preparation method substantially with embodiment 1, unlike, adding
Add and bismuth is added in agent ingredient, and makes the ratio 9:1:1:1 of gallium, indium, tin, bismuth；Specifically: at room temperature, by gallium 9g, metal
Indium 1g, metallic tin 1g, bismuth metal 1g are added in mortar, and grinding stirring 12 hours or so is to get additive.
Zinc-base battery is placed and nickel-zinc cell and carried out corresponding electric according to method provided by the present invention with additive
Performance test, it is as a result as follows: in 2C charge and discharge, to stablize specific capacity and be greater than 550mAh/g；Under above-mentioned multiplying power when charge and discharge,
Capacity can keep the 100% of initial capacity after 500 repeated charges.
The present invention for the zinc oxide electric conductivity generated in nickel-zinc cell charge and discharge process is low and poor circulation present in
Deficiency, by adding zinc-base battery additive, final obtain has high capacity, high rate capability and cycle performance excellent
Nickel-zinc cell.This has very important significance to the development and solution energy shortage etc. that push long circulating nickel-zinc cell.
Above example is only that a specific embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, those skilled in the art can also do numerous modifications and variations on the basis of existing technology, not depart from design of the present invention
Under the premise of spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (9)
1. a kind of additive of zinc-base battery, which is characterized in that the additive is metal, alloy and its oxide or hydrogen-oxygen
One of compound is a variety of；
The metal is one of gallium, indium, tin, lead, bismuth or a variety of；
The alloy is one of gallium, indium, tin, lead, the binary in bismuth or multicomponent alloy or a variety of；
The metal oxide is one of oxide of gallium, indium, tin, lead, bismuth or a variety of；
The hydroxide is one of hydroxide of gallium, indium, tin, lead, bismuth or a variety of.
2. additive according to claim 1, which is characterized in that the alloy is selected from gallium-indium alloy, gallium-indium-tin alloy, gallium
Indium bismuth alloy, gallium indium metal, gallium indium sn-bi alloy.
3. additive according to claim 1, which is characterized in that be grouped as by the group of following parts by weight: gallium/metal
Indium/1-11 parts of metallic tin, 0-1 parts of bismuth metal, 0-1 parts of metallic lead；Wherein gallium, indium metal, metallic tin mass ratio be (0-
9): (0-5): (0-1), and three is not 0 simultaneously.
4. additive according to claim 1, which is characterized in that be grouped as by the group of following parts by weight: gallium 5-9
Part, 1-5 parts of indium metal, 0-1 parts of metallic tin, 0-1 parts of bismuth metal, 0-1 parts of metallic lead.
5. additive according to claim 1, which is characterized in that be grouped as by the group of following parts by weight: gallium 7-9
Part, 1-2 parts of indium metal, 1 part of metallic tin, 0-1 parts of bismuth metal.
6. additive according to claim 1, which is characterized in that the state of the additive is liquid, powder or block.
7. application of any additive of claim 1-6 in zinc-base battery, the zinc-base battery is that can fill zinc-nickel, zinc-
One of air, zinc-manganese, silver-zinc battery；Nickel-zinc battery and the zinc-manganese battery of filling is excellent for large-scale energy-accumulating power station
Select wind energy, solar energy, tide energy clean energy resource peak load regulation network.
8. a kind of application method of any addition of claim 1-6, which is characterized in that the additive is placed in positive, negative
The position that pole, diaphragm or other electrolyte can contact.
9. application method according to claim 8, which is characterized in that the negative electrode material of the additive and zinc-base battery
Quality accounting is 0.1~20:100.
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