CN107634192A - A kind of zinc-base negative electrode battery material and preparation method thereof - Google Patents
A kind of zinc-base negative electrode battery material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of zinc-base negative electrode battery material, and the negative material is the structure of graphene sheet layer coating zinc oxide particle, and the quality accounting of zinc oxide is 60~95% in negative material；The thickness of graphene sheet layer is 0.5~10nm, and the planar dimension of graphene is 500nm~50 μm.The present invention also proposes the preparation method of the negative material.The present invention uses low-cost zinc oxide or its precursor salt and graphene oxide as raw material；The zinc-base negative electrode battery material with graphene coated zinc oxide structures is prepared using simple hydro-thermal method, solvent-thermal method or coprecipitation.The zinc-base battery for making negative pole assembling using graphene coated zinc oxide composite has 1.2~1.8V output voltages；Specific capacity when gained graphene coated zinc oxide composite is used as zinc-base cell negative electrode material is big, has super good cycle performance.
Description
Technical field
The invention belongs to carbon material preparation field, and in particular to a kind of preparation method of graphene.
Background technology
As increasingly sharpening for environmental pollution is increasingly exhausted with fossil energy, sustainable development is to novel renewable energy
Requirement improve constantly.Wherein, chargeable zinc-base battery is with its excellent specific property, and turns into electric automobile, Emergency power source, storage
The first choice of the energy storage devices such as energy power station, and future space technology and the preferable potential power-supply system of high-end energy-storage system.It can fill
Electric zinc-nickel cell is mainly made up of positive pole, negative pole, barrier film and electrolyte, and with high charge storage density, fast charging and discharging
The system of the chargeable zinc-base battery novel anode material of feature, good efficiency for charge-discharge and high circulation life-span and low cost
Standby is one of current most active branch of this research direction.
The advantages of zinc oxide often with negative material there is raw material easily to obtain, is cheap, environment-friendly as zinc-base battery,
It is the most commonly used zinc-base cell negative electrode material of research.But zinc oxide is poor in alkaline environment stability inferior, soluble, deformation,
Zhi Jing is easily formed in charge and discharge process, and the shortcomings that poorly conductive so that specific capacity be present as zinc-base cell negative electrode material in it
Low, the shortcomings that cyclical stability is poor.Therefore, the research in this current field concentrates on high power capacity, high power, long-life, low cost
In the research of new zinc base battery negative material, exploitation and technology of preparing.
Graphene is a kind of new two-dimensional material, has the advantages that specific surface area is big, good conductivity, Stability Analysis of Structures, closely
By the extensive concern in energy storage field over year.And graphene coated zinc oxide has electrical conductivity height, specific surface area is big, stability is good
The advantages of, it can effectively suppress zinc oxide dissolving and deformation, while can effectively disperse charging and discharging currents, surface current density is reduced, from
And suppress the brilliant formation of branch, and then improve cyclical stability.Therefore high ratio will be shown as zinc-base cell negative electrode material
Capacity, high rate capability, long circulation life.But the limited preparation method of the limited preparation method of current graphene coated zinc oxide
Still limit its practical application.
The content of the invention
The technical problems to be solved by the invention are to overcome the low yield of existing graphene production method, pollute big, technique
In place of the deficiencies of complicated, there is provided a kind of production cost is low, environment-friendly, yield is high and is suitable to the liquid phase of industrialized production peels off system
The method of standby graphene.
The technical scheme for realizing the object of the invention is：
A kind of zinc-base negative electrode battery material, the negative material are the structure of graphene sheet layer coating zinc oxide particle,
The quality accounting of zinc oxide is 60~95% in negative material；The thickness of graphene sheet layer is 0.5~10nm, the plane of graphene
Size is 500nm~50 μm.
Clad structure proposed by the present invention is original with graphene oxide (graphene) and zinc oxide (or zinc oxide precursor)
Material, is prepared by hydro-thermal method, solvent-thermal method or coprecipitation., can when the composite is used as zinc-base cell negative electrode material
Inverse capacity is 300~650mAh/g.
The preparation method of zinc-base negative electrode battery material of the present invention, including step：
(1) zinc compound and graphite material are dispersed in water and/or organic solvent, then in normal pressure reactor or
Reacted in water heating kettle, reaction temperature is 25~300 DEG C, and the mass ratio that feeds intake of wherein zinc compound and graphite material is
0.8~12:1；
The zinc compound is zinc oxide or zinc oxide precursor, and the zinc oxide precursor is selected from zinc salt, zinc-base water
One kind in talcum, organic matter containing zinc；The graphite material is graphene or graphene oxide；Described organic solvent is second
One or more combinations in alcohol, propyl alcohol, ethylene glycol, isopropanol, methyl pyrrolidone；The reaction is hydro-thermal reaction, molten
It is one or more in agent thermal response, coprecipitation reaction；
(2) use selected from any of vacuum drying, freeze-drying and supercritical drying seasoning to step (1)
Product system be dried.
Wherein, in step (1), the zinc oxide is by calcination method, solvent-thermal method, hydro-thermal method, coprecipitation, vapour deposition process
Preparation method in one kind be prepared, zinc oxide size is 10nm~50 μm；The zinc salt is zinc nitrate, zinc acetate, chlorine
Change the one or more in zinc, zinc sulfate, zinc stannate；The zinc-base hydrotalcite is zinc-aluminum hydrotalcite, zinc-aluminum-magnesium hydrotalcite, zinc-aluminium
One or more in copper water talcum, zinc-aluminium cerium hydrotalcite, zinc-aluminium lanthanum hydrotalcite.
Further, the graphite material is graphene oxide, and the graphite oxide is prepared with improved hummers ' methods,
Specially：Graphite flake and sodium nitrate are well mixed, the concentrated sulfuric acid is added, KMnO is slowly added under the conditions of less than 4 DEG C4, and
Stirring reaction 1h at a temperature of less than 4 DEG C, 30~40 DEG C of 0.5~1h of reaction are then heated to, deionized water is then slowly added into, treats
Deionized water is heated to seething with excitement after being added completely into, and keeps reacting 30min；Wherein graphite flake, sodium nitrate, the concentrated sulfuric acid, KMnO4,
Mass ratio be 1：0.1~0.8：20~50：2~4.
When the middle zinc oxide or zinc oxide precursor using selected by coprecipitation of step (1) can not be total to graphene oxide
During precipitation, using additive；When forerunner's physical efficiency employed in step (1) is co-precipitated with graphene oxide, additive can add
It can be not added with.
Further, it is added with additive, the additive in the dispersion of the zinc compound and graphite material
Silane coupler and/or surfactant；Selected from aminopropyl triethoxysilane, CTAB, lauryl sodium sulfate (SDS),
One or more in PVP, F127 etc., the mass ratio of the additive and zinc compound is 1：0.8~1.5.
As a preferred technical solution of the present invention, step (1) is：Zinc oxide is dispersed in water, adds additive,
Stirring 10~30 hours；Graphite material is dispersed in water, burnett's solution is slowly added in the aqueous solution of graphite material, room
Temperature stirring makes it be co-precipitated 2~4 hours.Feed postition can be added dropwise or be poured slowly into.
, it is necessary to add reducing agent when solvent employed in step (1) does not have reproducibility；Adopted when in step (1)
When solvent has reproducibility, reducing agent, which can add, to be not added with.
Further, after step (1) forms dispersion, it is anti-reduce that reducing agent is added into the dispersion
Answer, one or more of the reducing agent in hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen, the temperature of reduction reaction is
50 DEG C~90 DEG C.
Alternatively, after step (2), products therefrom is heat-treated, treatment temperature is 200~1000 DEG C, processing
Time is 0.5~10 hour.
Battery containing zinc-base negative electrode battery material of the present invention.
Described battery, its negative pole preparation method are：Negative material, binder, conductive agent mixing described in claim 1
Afterwards, it is coated with a current collector；The just extremely nickel hydroxide of the battery.
The binder, conductive agent can use the existing binder in this area and conductive agent, such as PTFE, acetylene black, super
Level carbon black etc., the collector can be one kind in copper mesh, copper foil, aluminium foil, but not limited to this.
The present invention has the following advantages that compared with prior art：
(1) present invention uses low-cost zinc oxide or its precursor salt and graphene oxide as raw material；(2) using simple
Hydro-thermal method, solvent-thermal method or coprecipitation prepare the zinc-base negative electrode battery material with graphene coated zinc oxide structures
Material.(3) the zinc-base battery for making negative pole assembling using graphene coated zinc oxide composite has 1.2~1.8V output voltages；
(4) specific capacity when gained graphene coated zinc oxide composite is used as zinc-base cell negative electrode material is greatly (in 1C discharge and recharges
Specific capacity can reach 300~700mAh/g)；(5) gained graphene coated zinc oxide composite is used as Zinc-nickel battery negative material
There is super good cycle performance (to remain to keep 200-500mAh/ after 100 repeated charges under the conditions of 1C discharge and recharges during material
g)。
To sum up, composite of the invention has high electric conductivity, has super excellent high rate capability and well follows
Ring stability, it is ideal zinc-base cell negative electrode material, can be widely applied to various portable electric appts, electric automobile
And the field such as Aero-Space；In addition, the composite can from low-cost raw material, by it is repeated it is high, process is simple,
Take few technique to prepare, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the material of embodiment 2.
Fig. 2 is the reversible charging and discharging curve of embodiment 2.
Fig. 3 is the stereoscan photograph of the material of embodiment 6.
Fig. 4 is the XRD spectrum of the material of embodiment 6.
Embodiment
Detailed description below is used to illustrate the present invention, but should not be construed as limiting the invention.
The preparation method of graphene oxide is improved hummers ' methods in embodiment.By 10g graphite flakes and 5g sodium nitrate
It is well mixed, the 220mL concentrated sulfuric acids are added, less than 4 DEG C, 30g KMnO are slowly added under conditions of stirring, within 30min4, so
The stirring reaction 1h at less than 4 DEG C afterwards, 35 DEG C of reaction 30min are then warming up to, are then slowly added into 450mL deionizations
Water, but after water is added completely into, be heated to seething with excitement, and keep reacting 30min, then through supercooling, is washed, dialysis, concentration and cold
Freeze dry acquisition graphene oxide.
Observed through SEM, 0.5~10nm of obtained graphene oxide layer thickness, planar dimension is 500nm~50 μm.
The calcination method zinc oxide used in embodiment is purchased in market, and particle diameter distribution is in 10 nanometers~50 μm sections.
In embodiment, unless otherwise instructed, technological means used is this area conventional technology.
Embodiment 1：
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) by zinc oxide 80g obtained by calcination method and graphene oxide 20g, (the two mass ratio is 4:1) mix, be distributed to
In 5000g water, then it is sealed in water heating kettle, at 150 ± 5 DEG C, reacts 12 hours or so；
(2) 5000g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product, as graphene coated zinc oxide composites are freeze-dried to obtain at a temperature of (3) -50 DEG C.
Graphene coated zinc oxide obtained by the present embodiment has three-dimensional net structure, and three dimensional gel net is formed by graphene
Network, size are that to be coated on thickness be 0.5~10nm to the Zinc oxide particles of 10nm~50 μm, and planar dimension is 500nm~50 μm
Inside graphene sheet layer.
Embodiment 2
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) 0.5g graphene oxides are dispersed in 1000g water, zinc oxide obtained by 20g calcination methods is separately dispersed in 200g
In water, zinc oxide aqueous solution is slowly added in graphene oxide water solution, being stirred at room temperature makes it be co-precipitated 3 hours；
(2) 500g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product, as graphene coated zinc oxide composites are freeze-dried to obtain at a temperature of (3) -50 DEG C.
The present embodiment is different from embodiment 1, prepares graphene coated zinc oxide using coprecipitation, uses scanning electron microscopy
Mirror characterizes its pattern as shown in figure 1, resulting graphene coated zinc oxide composite is by thin pliable graphene sheet layer
It is complete to be coated on the zinc oxide particle surfaces composition that size is 10nm~50 μm, and Zinc oxide particles are evenly distributed.Zinc oxide is not
Doping is also realized forms composite with graphene, but covered effect is not as additivated.
The reversible charging and discharging curve that the present embodiment material forms full battery is as shown in Figure 2.
Embodiment 3
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) by 0.5g graphene dispersions in 1000g water, separately zinc oxide obtained by 20g calcination methods is dispersed in 200g water,
Zinc oxide aqueous solution is slowly added in graphene oxide water solution, being stirred at room temperature makes it be co-precipitated 3 hours；
Solid product, as graphene coated zinc oxide composites are freeze-dried to obtain at a temperature of (2) -50 DEG C.
The embodiment is different from embodiment 2, and using graphene as raw material, coprecipitation prepares graphene coated oxidation
Zinc, it is not necessary to which the step of electronation graphene oxide, resulting graphene coated zinc oxide composite is by thin pliable
Graphene sheet layer be completely coated on the zinc oxide particle surfaces that size is 10nm~50 μm and form, and Zinc oxide particles distribution is equal
It is even.
Embodiment 4
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1), zinc oxide obtained by 20g calcination methods is dispersed in 200g water, adds 20g aminopropyl trimethoxysilanes, room
Temperature stirring 24 hours；
(2) 0.5g graphene oxides are dispersed in 1000g water, the system Jing Guo step (1) is slowly added to aoxidize stone
In black aqueous solution, being stirred at room temperature makes it be co-precipitated 3 hours；
(3) 500g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product, as graphene coated zinc oxide composites are freeze-dried to obtain at a temperature of (4) -50 DEG C.
Graphene coated zinc oxide composite obtained by the embodiment has a graphene coated zinc oxide structures, it is thin and
Soft graphene sheet layer is completely coated on the zinc oxide particle surfaces that size is 10nm~50 μm, and Zinc oxide particles distribution is equal
It is even.
Embodiment 5
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) zinc oxide obtained by 20g coprecipitations (prepared by laboratory, particle diameter 10nm~1 μm) is dispersed in 200g water, added
Enter 20g SDS, be stirred at room temperature 24 hours；
(2) 0.5g graphene oxides are dispersed in 1000g water, the system Jing Guo step (1) is slowly added to aoxidize stone
In black aqueous solution, being stirred at room temperature makes it be co-precipitated 3 hours；
(3) 500g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product, as graphene zinc oxide composites are freeze-dried to obtain at a temperature of (4) -50 DEG C.
Graphene coated zinc oxide composite obtained by the embodiment has a graphene coated zinc oxide structures, it is thin and
Soft graphene sheet layer is completely coated on the zinc oxide particle surfaces that size is 10nm~50 μm, and Zinc oxide particles distribution is equal
It is even.
Embodiment 6
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1), 0.5g graphene oxides are dispersed in 1000g water, separately 40g zinc nitrates are dispersed in 200g water, by nitre
The sour zinc aqueous solution is slowly added in graphene oxide water solution, and being stirred at room temperature makes it be co-precipitated 3 hours；
(2) 500g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product is freeze-dried to obtain at a temperature of (3) -50 DEG C；
(4) by the solid product Jing Guo step (3) in the tube furnace that nitrogen makees protective atmosphere at 500 DEG C calcining is 2 small
When, obtain graphene coated zinc oxide composite.
Graphene coated zinc oxide composite obtained by the present embodiment is characterized using SEM, as shown in figure 3,
Gained composite has graphene coated zinc oxide structures, and it is 10nm that thin pliable graphene sheet layer, which is completely coated on size,
~200nm zinc oxide particle surfaces, and Zinc oxide particles are evenly distributed.Prove that it has ZnO knots using X-ray diffraction analysis
Structure, as shown in Figure 4.
Embodiment 7
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) zinc-aluminum hydrotalcite 30g and graphene oxide 20g is mixed, is distributed in 5000g water, is then sealed in hydro-thermal
In kettle, at 150 ± 5 DEG C, react 12 hours or so；
(2) 5000g hydrazine hydrates are added in the product system obtained to step (1), reduction reaction is carried out at 60 ± 2 DEG C,
Reaction 2 hours or so；
Solid product is freeze-dried to obtain at a temperature of (3) -50 DEG C.
(4) by the solid product Jing Guo step (3) in the tube furnace that nitrogen makees protective atmosphere at 500 DEG C calcining is 2 small
When, obtain graphene coated zinc oxide composite.
Graphene coated zinc oxide obtained by the present embodiment has three-dimensional net structure, and three dimensional gel net is formed by graphene
Network, size are that to be coated on thickness be 0.5~10nm to the Zinc oxide particles of 10nm~50 μm, and planar dimension is 500nm~50 μm
Inside graphene sheet layer.
Embodiment 8
A kind of graphene coated zinc oxide composite, it is made by the steps to obtain：
(1) 0.5g graphene oxides are dispersed in 1000g water, separately 40g zinc acetates is dispersed in 200g water, by acetic acid
The zinc aqueous solution is slowly added in graphene oxide water solution, and being stirred at room temperature makes it be co-precipitated 3 hours；
(2) 500g hydrazine hydrates are added into the system by step (1), reduction reaction, reaction 2 are carried out at 60 ± 2 DEG C
Hour or so；
Solid product is freeze-dried to obtain at a temperature of (3) -50 DEG C；
(4) by the solid product Jing Guo step (3) in the tube furnace that nitrogen makees protective atmosphere at 500 DEG C calcining is 2 small
When, obtain graphene coated zinc oxide composite.
Graphene coated zinc oxide composite obtained by the embodiment has a graphene coated zinc oxide structures, it is thin and
Soft graphene sheet layer is completely coated on the zinc oxide particle surfaces that size is 10nm~50 μm, and Zinc oxide particles distribution is equal
It is even.
Cycle performance is tested
Following steps are taken to prepare zinc-base GND working electrode：
(1) graphene coated zinc oxide composite, binder PTFE, acetylene black are pressed 8：1：1 ratio is well mixed,
Uniformly it is applied to after being modulated into paste with deionized water on brass screen；
(2) dried 12 hours at 80 DEG C in vacuum drying oven；
(3) brass screen for scribbling graphene coated zinc oxide composite is cut into disk and working electrode is made.
It is as follows to the method for testing of the chemical property of electrode material：
(1) simulated battery is using button CR2032 type systems, wherein just extremely spherical Ni (OH)2。
(2) reversible capacity of electrode material, coulombic efficiency, cycle performance, experiment carry out test point using constant current charge-discharge
Analysis.Discharge and recharge system is：Voltage range：1.0-1.9V；Cycle-index is generally 1-3000 times.
The full battery of above-described embodiment 1-8 materials composition, cycle charge discharge electrical property inspection table 1.
Table 1：Embodiment 1-8 material charge-discharge performances
Deficiency of the present invention present in for zinc oxide poorly conductive and poor circulation, by preparation method and prepares bar
The control of part, final chargeable zinc-base battery of the acquisition with ultra-high capacity, ultra-high magnifications performance and super good cycle performance are used negative
Pole material.This has very important significance to promoting the development of high-performance zinc-base battery and solving energy shortage etc..
Example above is only that the embodiment of the present invention is described, and not the scope of the present invention is carried out
Limit, those skilled in the art can also do numerous modifications and variations, not depart from design of the present invention on the basis of existing technology
On the premise of spirit, all variations and modifications that this area ordinary skill technical staff makes to technical scheme,
It should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of zinc-base negative electrode battery material, it is characterised in that the negative material is graphene sheet layer coating zinc oxide
The structure of grain, the quality accounting of zinc oxide is 60~95% in negative material；The thickness of graphene sheet layer is 0.5~10nm, stone
The planar dimension of black alkene is 500nm~50 μm.
2. the preparation method of zinc-base negative electrode battery material described in claim 1, it is characterised in that including step：
(1) zinc compound is dispersed in water and/or organic solvent with graphite material, then in normal pressure reactor or hydro-thermal
Reacted in kettle, reaction temperature is 25~300 DEG C, wherein the mass ratio that feeds intake of zinc compound and graphite material for 0.8~
12:1；
The zinc compound is zinc oxide or zinc oxide precursor, the zinc oxide precursor be selected from zinc salt, zinc-base hydrotalcite,
One kind in organic matter containing zinc；The graphite material is graphene or graphene oxide；Described organic solvent is ethanol, third
One or more combinations in alcohol, ethylene glycol, isopropanol, methyl pyrrolidone；The reaction is hydro-thermal reaction, solvent heat is anti-
Answer, be one or more in coprecipitation reaction；
(2) using selected from production of the seasoning to step (1) of any of vacuum drying, freeze-drying and supercritical drying
Objects system is dried.
3. graphene coated zinc oxide composite according to claim 2, it is characterised in that：In step (1), the oxygen
Change zinc to be prepared by one kind in calcination method, solvent-thermal method, hydro-thermal method, coprecipitation, the preparation method of vapour deposition process, oxygen
It is 10nm~50 μm to change zinc size；The zinc salt is zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, one kind in zinc stannate or more
Kind；The zinc-base hydrotalcite is zinc-aluminum hydrotalcite, zinc-aluminum-magnesium hydrotalcite, zinc-aluminium copper water talcum, zinc-aluminium cerium hydrotalcite, zinc-aluminium lanthanum water
One or more in talcum.
4. preparation method according to claim 2, it is characterised in that the graphite material is graphene oxide, the oxygen
Graphite is prepared with improved hummers ' methods, is specially：Graphite flake and sodium nitrate are well mixed, the concentrated sulfuric acid is added, low
KMnO is slowly added under the conditions of 4 DEG C4, and the stirring reaction 1h at a temperature of less than 4 DEG C, then heat to 30~40 DEG C of reactions
0.5~1h, deionized water is then slowly added into, is heated to seething with excitement after deionized water is added completely into, and keep reacting 30min；
Wherein graphite flake, sodium nitrate, the concentrated sulfuric acid, KMnO4, mass ratio be 1：0.1~0.8：20~50：2~4.
5. preparation method according to claim 2, it is characterised in that the dispersion of the zinc compound and graphite material
In system aminopropyl triethoxysilane, CTAB, lauryl sodium sulfate, PVP, F127 are selected from added with additive, the additive
One or more in, the mass ratio of the additive and zinc compound is 1：0.8~1.5.
6. according to the preparation method described in any one of claim 2~5, it is characterised in that step (1) is：Zinc oxide is disperseed
In water, additive is added, is stirred 10~30 hours；Graphite material is dispersed in water, burnett's solution is slowly added to stone
In the aqueous solution of ink material, being stirred at room temperature makes it be co-precipitated 2~4 hours.
7. preparation method according to claim 2, it is characterised in that after step (1) forms dispersion, disperse to described
Reducing agent is added in system to carry out reduction reaction, the reducing agent is in hydrazine hydrate, sodium borohydride, potassium borohydride, hydrogen
One or more, the temperature of reduction reaction is 50 DEG C~90 DEG C.
8. preparation method according to claim 2, it is characterised in that after step (2), hot place is carried out to products therefrom
Reason, treatment temperature are 200~1000 DEG C, and processing time is 0.5~10 hour.
9. the battery containing the zinc-base negative electrode battery material described in claim 1.
10. battery according to claim 9, it is characterised in that the negative pole preparation method of the battery is：Claim 1
After the negative material, binder, conductive agent mixing, coating is on a current collector；The just extremely nickel hydroxide of the battery.
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| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN113611828A (en) * | 2021-07-16 | 2021-11-05 | 山东合泰新能源有限公司 | Zinc oxide composite material, preparation method thereof, negative electrode zinc paste and zinc-nickel storage battery |
| CN113611828B (en) * | 2021-07-16 | 2023-10-24 | 山东合泰新能源有限公司 | Zinc oxide composite material, preparation method, negative electrode zinc paste and zinc-nickel storage battery |
| CN113745520A (en) * | 2021-09-05 | 2021-12-03 | 浙江大学 | Preparation method and application of zinc cathode material for inhibiting zinc dendrites |
| CN113745520B (en) * | 2021-09-05 | 2022-12-13 | 浙江大学 | Preparation method and application of zinc cathode material for inhibiting zinc dendrites |
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Effective date of registration: 20210308 Address after: 453000 the southeast corner of the intersection of national highway 107 and Deyuan road in Xinxiang City, Henan Province passes through A1B and A1C of Filter Industrial Park in high tech Zone Patentee after: Henan Chaoli New Energy Co.,Ltd. Address before: 100191 No. 37, Haidian District, Beijing, Xueyuan Road Patentee before: BEIHANG University |