CN107394151B - A kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide - Google Patents

A kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide Download PDF

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CN107394151B
CN107394151B CN201710578924.3A CN201710578924A CN107394151B CN 107394151 B CN107394151 B CN 107394151B CN 201710578924 A CN201710578924 A CN 201710578924A CN 107394151 B CN107394151 B CN 107394151B
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zinc oxide
cathode material
battery cathode
porous carbon
nanocapsule
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CN107394151A (en
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李明强
崔超
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Dalian University of Technology
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Dalian University of Technology
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 provides a kind of preparation method of nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide, at room temperature, after zinc oxide, dehydrated alcohol, deionized water are mixed, Resorcino, formaldehyde is added, stirring makes it sufficiently polymerize cladding；It will be placed in tube furnace after solid centrifugation, filtering, drying, 600~1200 DEG C of progress carbonization treatments are heated in nitrogen atmosphere, it is passed through carbon dioxide gas again and carries out activation 1~5h of pore-creating, the nickel zinc battery cathode material of the porous carbon nanocapsule of in-stiu coating zinc oxide is obtained after finally cooling down.Present invention firstly provides the nickel zinc battery cathode material that the preparation of in-stiu coating method has the porous carbon nanocapsule of the in-stiu coating zinc oxide of excellent electric conductivity, high pore volume and Large ratio surface, zinc oxide is fixed in capsule by carbon atom, avoids its dissolution；The micropore that size can be regulated and controled on carbon cyst wall can make the alkali anion of small size free in and out carbon capsule, have good application value and market prospects.

Description

A kind of nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide Preparation method
Technical field
The present invention relates to field of batteries, provide a kind of for the nickel zinc electricity based on porous carbon nanocapsule in-stiu coating zinc oxide Pond negative electrode material and preparation method thereof.
Background technique
Nickel-zinc cell is a kind of High-performance green secondary power battery, has specific energy high, low temperature performance well and memoryless Effect.It not can cause environmental pollution in the production and use process, be known as real " green battery ", there is wide grind Study carefully prospect.The electrochemical reaction of Ni-MH secondary battery is the reaction carried out in alkaline solution, the reaction speed of zinc mainly by Liquid phase diffusing step influences.
At this stage, because in nickel-zinc cell macroscopic property it is unstable, cause to charge product zincate and discharging product ZnO exist The problems such as being dissolved in alkaline solution, thus causing zinc load deformation, dendritic growth and passivation and self-corrosion, so that electrode failure With the decaying of battery cycle life.
Summary of the invention
The present invention to solve the above-mentioned problems, provides a kind of with excellent electric conductivity, high pore volume and Large ratio surface Porous carbon nanocapsule in-stiu coating zinc oxide, prepares the negative electrode material of nickel-zinc cell, which can be avoided zinc oxide Dissolution and enhancing electronic conductivity and ion diffusion rates, obtain big specific capacity, long circulating stability and high rate capability.
The porous carbon nanocapsule of the negative electrode material can envelope zinc oxide, can regulate and control the micro- of size on nanocapsule Hole can allow alkali to free in and out carbon capsule again, and the zinc oxide of macromolecular is then fixed on and intracapsular cannot come out.Carbon material tool simultaneously There is excellent electric conductivity.And then the nickel-zinc cell of big specific capacity, long circulating stability and high rate capability is obtained, have extensive Application prospect.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide, including with Lower step:
At room temperature, after zinc oxide, dehydrated alcohol, deionized water being mixed, Resorcino, formaldehyde, stirring 12 is added ~48 hours, it is made sufficiently to polymerize cladding；It will place in tube furnace after solid centrifugation, filtering, drying, heated in nitrogen atmosphere It to 600~1200 DEG C of progress 2~10h of carbonization treatment, then is passed through carbon dioxide gas and carries out activation 1~5h of pore-creating, finally cool down The nickel zinc battery cathode material of the porous carbon nanocapsule of in-stiu coating zinc oxide is obtained afterwards.
In order to control the aperture of nanocapsule at 3 nanometers hereinafter, the throughput for being passed through carbon dioxide gas be 100~ 300 milliliters per minute.
The zinc oxide, dehydrated alcohol, deionized water mass ratio be 1:1~8:1~8.
The zinc oxide, Resorcino, formaldehyde mass ratio be 1:0.1~1:0.1~1.
The nickel zinc battery cathode material is the adjustable porous carbon nanocapsule coating zinc oxide in aperture.
The beneficial effects of the present invention are: present invention firstly provides the preparations of in-stiu coating method to have excellent electric conductivity, Gao Kong The nickel zinc battery cathode material of the porous carbon nanocapsule of the in-stiu coating zinc oxide of volume and Large ratio surface, aperture are adjustable more Hole carbon nanocapsule imparts the ability being encapsulated in high carrying capacity zinc oxide in carbon capsule.Zinc oxide can be fixed on capsule by carbon atom In, avoid its dissolution；The micropore that size can largely be regulated and controled on carbon cyst wall can be controlled in 3 nanometers hereinafter, making small size Alkali anion can free in and out carbon capsule.Since carbon material is low in cost, before there is certain application value and market Scape provides possibility for nickel-zinc cell industrialization.
Detailed description of the invention
Fig. 1 is the electron microscopic picture of the target material of 200,000 times of amplification；
Fig. 2 is the electron microscopic picture of the target material of 100 hundred million times of amplification.
Specific embodiment
The present invention will be further described below.
Embodiment 1
3g zinc oxide and 10 grams of ethyl alcohol are added into 1g Resorcino after 10 grams of deionized waters are mixed 1 hour, Solid after stirring 12 hours, is taken out centrifugal filtration drying, it is small to heat two in nitrogen atmosphere with tube furnace by 1.12 gram liter formaldehyde Up to 600 degree, carbonization 2 hours is maintained, then be passed through and carry out within carbon dioxide 1 hour activation pore-creating, throughput maintains 300 milliliters often Minute to control the aperture of nanocapsule at 3 nanometers or less.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.
Embodiment 2
1.5g zinc oxide and 10 grams of ethyl alcohol are added into hexichol between 0.8g after 12 grams of deionized waters are mixed 1 hour Solid after stirring 24 hours, is taken out centrifugal filtration drying, heats two in nitrogen atmosphere with tube furnace by phenol, 1.12 grams of formaldehyde Hour maintains carbonization 4 hours to 600 degree, then is passed through carbon dioxide 2 hours and carries out activation pore-creating, and throughput maintains 300 milliliters Per minute to control the aperture of nanocapsule at 3 nanometers or less.The porous carbon nanometer of in-stiu coating zinc oxide is just obtained after cooling The nickel zinc battery cathode material of capsule.
Embodiment 3
3g zinc oxide and 10 grams of ethyl alcohol are added into 0.8g Resorcino after 12 grams of deionized waters are mixed 1 hour, Solid after stirring 40 hours, is taken out centrifugal filtration drying, is heated in nitrogen atmosphere two hours with tube furnace by 1.12 grams of formaldehyde To 900 degree, carbonization 4 hours is maintained, then be passed through carbon dioxide 3 hours and carry out activation pore-creating, throughput maintains 100 milliliters every point Clock is to control the aperture of nanocapsule at 3 nanometers or less.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.
Embodiment 4
5g zinc oxide and 10 grams of ethyl alcohol are added into 0.8g Resorcino after 12 grams of deionized waters are mixed 1 hour, Solid after stirring 36 hours, is taken out centrifugal filtration drying, is heated in nitrogen atmosphere two hours with tube furnace by 1.12 grams of formaldehyde To 1000 degree, carbonization 8 hours is maintained, then be passed through and carry out within carbon dioxide 5 hours activation pore-creating, throughput maintains 200 milliliters often Minute to control the aperture of nanocapsule at 3 nanometers or less.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.

Claims (2)

1. a kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide, feature exist In following steps:
At room temperature, after zinc oxide, dehydrated alcohol, deionized water being mixed, after Resorcino, formaldehyde is added, stirring makes it Sufficiently polymerization cladding；It will be placed in tube furnace after solid centrifugation, filtering, drying, 600~1200 DEG C be heated in nitrogen atmosphere 2~10h of carbonization treatment is carried out, then is passed through carbon dioxide gas and carries out activation 1~5h of pore-creating, obtains in-stiu coating after finally cooling down The nickel zinc battery cathode material of the porous carbon nanocapsule of zinc oxide；
The zinc oxide, dehydrated alcohol, deionized water mass ratio be 1:1~8:1~8；
The zinc oxide, Resorcino, formaldehyde mass ratio be 1:0.1~1:0.1~1；
The throughput for being passed through carbon dioxide gas is 100~300 milliliters per minute, is controlled in nickel zinc battery cathode material Nanocapsule aperture at 3 nanometers or less.
2. a kind of nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide according to claim 1 Preparation method, which is characterized in that the described mixing time that mixed liquor after Resorcino, formaldehyde is added is 12~48 hours.
CN201710578924.3A 2017-07-18 2017-07-18 A kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide Active CN107394151B (en)

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CN111952549B (en) * 2019-05-16 2021-08-17 宝山钢铁股份有限公司 Carbon-coated lithium battery negative electrode material with yolk-eggshell structure and preparation method thereof
CN113023768A (en) * 2021-03-02 2021-06-25 东北大学 ZnO @ C negative electrode material for zinc-nickel battery and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103606657A (en) * 2013-12-10 2014-02-26 北京理工大学 Lithium ion battery zinc oxide/porous carbon composite negative electrode material with high capacity and preparation method thereof
CN103794824A (en) * 2014-02-10 2014-05-14 湖南省科学技术研究开发院 Preparation method of alkaline secondary zinc-nickel storage battery
CN104627976A (en) * 2013-11-11 2015-05-20 天津得瑞丰凯新材料科技有限公司 Preparation method of meso-porous carbon aerogel with high specific surface area
CN106241857A (en) * 2016-08-18 2016-12-21 江苏万祥锌业有限公司 A kind of nano zine oxide preparation technology

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KR101641483B1 (en) * 2014-08-01 2016-07-22 서울과학기술대학교 산학협력단 MANUFACTURE METHOD OF POCKET TYPE Ni-Zn BATTERY

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Publication number Priority date Publication date Assignee Title
CN104627976A (en) * 2013-11-11 2015-05-20 天津得瑞丰凯新材料科技有限公司 Preparation method of meso-porous carbon aerogel with high specific surface area
CN103606657A (en) * 2013-12-10 2014-02-26 北京理工大学 Lithium ion battery zinc oxide/porous carbon composite negative electrode material with high capacity and preparation method thereof
CN103794824A (en) * 2014-02-10 2014-05-14 湖南省科学技术研究开发院 Preparation method of alkaline secondary zinc-nickel storage battery
CN106241857A (en) * 2016-08-18 2016-12-21 江苏万祥锌业有限公司 A kind of nano zine oxide preparation technology

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