CN107394151A - 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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Publication number
CN107394151A
CN107394151A CN201710578924.3A CN201710578924A CN107394151A CN 107394151 A CN107394151 A CN 107394151A CN 201710578924 A CN201710578924 A CN 201710578924A CN 107394151 A CN107394151 A CN 107394151A
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zinc oxide
cathode material
porous carbon
battery cathode
stiu coating
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CN201710578924.3A
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CN107394151B (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide, at room temperature, after zinc oxide, absolute ethyl alcohol, deionized water are mixed, adds Resorcino, formaldehyde, stirring makes it fully polymerize cladding；Solid is centrifuged, filtered, dry after place tube furnace in, 600~1200 DEG C of progress carbonization treatments are heated in nitrogen atmosphere, carbon dioxide is passed through again to carry out activating 1~5h of pore-creating, and the nickel zinc battery cathode material of the porous carbon nanocapsule of in-stiu coating zinc oxide is obtained after finally cooling down.The nickel zinc battery cathode material of the porous carbon nanocapsule of the in-stiu coating zinc oxide with excellent electric conductivity, high pore volume and Large ratio surface is prepared present invention firstly provides in-stiu coating method, zinc oxide is fixed in capsule by carbon atom, avoids its dissolving；The micropore of 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, provides a kind of nickel zinc electricity being used for based on porous carbon nanocapsule in-stiu coating zinc oxide Pond negative material and preparation method thereof.
Background technology
Nickel-zinc cell is a kind of High-performance green secondary power battery, has, low temperature performance well and memoryless higher than energy Effect.Environment will not be polluted in the production and use process, be described 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 decay of battery cycle life.
The content of the invention
The present invention is in order to solve the above problems, there is provided 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 material of nickel-zinc cell, and the negative material can avoid zinc oxide Dissolving and enhancing electronic conductivity and ion diffusion rates, obtain big specific capacity, long circulating stability and high rate capability.
The porous carbon nanocapsule of described negative 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 can not 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.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
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, absolute ethyl alcohol, deionized water being mixed, Resorcino, formaldehyde, stirring 12 are added ~48 hours, it is set fully to polymerize cladding；Solid is centrifuged, filtered, dry after place tube furnace in, heated in nitrogen atmosphere To 600~1200 DEG C of progress 2~10h of carbonization treatment, then it is passed through carbon dioxide and carries out activating 1~5h of pore-creating, finally cools 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 below 3 nanometers, the described throughput for being passed through carbon dioxide be 100~ 300 milliliters per minute.
Described zinc oxide, absolute ethyl alcohol, the mass ratio of deionized water are 1：1~8:1~8.
Described zinc oxide, Resorcino, the mass ratio of formaldehyde are 1:0.1~1:0.1~1.
Described nickel zinc battery cathode material is the adjustable porous carbon nanocapsule coating zinc oxide in aperture.
The beneficial effects of the invention are as follows：Present invention firstly provides in-stiu coating method to prepare with 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, its 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 dissolving；The micropore of size can largely be regulated and controled on carbon cyst wall can be controlled in less than 3 nanometers so that small size Alkali anion can free in and out carbon capsule.Because carbon material cost is cheap, therefore with before certain application value and market Scape, possibility is provided for nickel-zinc cell industrialization.
Brief description of the drawings
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.
Embodiment
The present invention will be further described below.
Embodiment 1
By 3g zinc oxide and 10 grams of ethanol, after 10 grams of deionized waters mix 1 hour, 1g Resorcinos are added, 1.12 gram liter formaldehyde, after stirring 12 hours, solid is taken out into centrifugal filtration drying, it is small that two are heated in nitrogen atmosphere with tube furnace Up to 600 degree, carbonization 2 hours is maintained, then is passed through carbon dioxide and carries out within 1 hour activation pore-creating, throughput maintains 300 milliliters often Minute to control the aperture of nanocapsule below 3 nanometers.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.
Embodiment 2
By 1.5g zinc oxide and 10 grams of ethanol, after 12 grams of deionized waters mix 1 hour, hexichol between 0.8g is added Phenol, 1.12 grams of formaldehyde, after stirring 24 hours, solid is taken out into centrifugal filtration drying, two are heated in nitrogen atmosphere with tube furnace Hour to 600 degree, maintains carbonization 4 hours, then is passed through carbon dioxide and carries out within 2 hours activation pore-creating, and throughput maintains 300 milliliters It is per minute to control the aperture of nanocapsule below 3 nanometers.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
By 3g zinc oxide and 10 grams of ethanol, after 12 grams of deionized waters mix 1 hour, 0.8g Resorcinos are added, 1.12 grams of formaldehyde, after stirring 40 hours, solid is taken out into centrifugal filtration drying, heated with tube furnace in nitrogen atmosphere two hours To 900 degree, carbonization 4 hours is maintained, then is passed through carbon dioxide and carries out within 3 hours activation pore-creating, throughput maintains 100 milliliters every point Clock is to control the aperture of nanocapsule below 3 nanometers.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.
Embodiment 4
By 5g zinc oxide and 10 grams of ethanol, after 12 grams of deionized waters mix 1 hour, 0.8g Resorcinos are added, 1.12 grams of formaldehyde, after stirring 36 hours, solid is taken out into centrifugal filtration drying, heated with tube furnace in nitrogen atmosphere two hours To 1000 degree, carbonization 8 hours is maintained, then is passed through carbon dioxide and carries out within 5 hours activation pore-creating, throughput maintains 200 milliliters often Minute to control the aperture of nanocapsule below 3 nanometers.The porous carbon nanocapsule of in-stiu coating zinc oxide is just obtained after cooling Nickel zinc battery cathode material.

Claims (3)

1. a kind of preparation method of the nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide, its feature exist In following steps：
At room temperature, after zinc oxide, absolute ethyl alcohol, deionized water being mixed, after adding Resorcino, formaldehyde, stirring, it is made Fully polymerization cladding；Solid is centrifuged, filtered, dry after place tube furnace in, 600~1200 DEG C are heated in nitrogen atmosphere 2~10h of carbonization treatment is carried out, then is passed through carbon dioxide and carries out activating 1~5h of pore-creating, in-stiu coating is obtained after finally cooling down The nickel zinc battery cathode material of the porous carbon nanocapsule of zinc oxide；
Described zinc oxide, absolute ethyl alcohol, the mass ratio of deionized water are 1：1~8:1~8；
Described zinc oxide, Resorcino, the mass ratio of formaldehyde are 1:0.1~1:0.1~1.
A kind of 2. nickel zinc battery cathode material based on porous carbon nanocapsule in-stiu coating zinc oxide according to claim 1 Preparation method, it is characterised in that the described throughput for being passed through carbon dioxide be 100~300 milliliters it is per minute, control The aperture of nanocapsule in nickel zinc battery cathode material is below 3 nanometers.
A kind of 3. cathode of nickel zinc battery based on porous carbon nanocapsule in-stiu coating zinc oxide according to claim 1 or 2 The preparation method of material, it is characterised in that it is described add mixed liquor after Resorcino, formaldehyde mixing time it is small for 12~48 When.
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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111952549A (en) * 2019-05-16 2020-11-17 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 (5)

* 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
KR20160017243A (en) * 2014-08-01 2016-02-16 서울과학기술대학교 산학협력단 MANUFACTURE METHOD OF POCKET TYPE Ni-Zn 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
KR20160017243A (en) * 2014-08-01 2016-02-16 서울과학기술대학교 산학협력단 MANUFACTURE METHOD OF POCKET TYPE Ni-Zn 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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111952549A (en) * 2019-05-16 2020-11-17 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
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

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