CN107146915B - A kind of preparation method of porous bismuth-carbon composite - Google Patents
A kind of preparation method of porous bismuth-carbon composite Download PDFInfo
- Publication number
- CN107146915B CN107146915B CN201710227930.4A CN201710227930A CN107146915B CN 107146915 B CN107146915 B CN 107146915B CN 201710227930 A CN201710227930 A CN 201710227930A CN 107146915 B CN107146915 B CN 107146915B
- Authority
- CN
- China
- Prior art keywords
- bismuth
- carbon cloth
- carbon composite
- carbon
- porous bismuth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of porous bismuth-carbon composite, include the following steps: that polyacrylonitrile is dispersed in dimethyl sulfoxide by S1., and bismuth salt is then added, and form sol precursor；S2. carbon cloth is immersed in S1 in sol precursor, heating, drying；S3. the carbon cloth for passing through heating, drying in S2 is impregnated in potassium hydroxide-ethanol solution, dries, porous bismuth-carbon composite is obtained after calcining；Sol precursor of the present invention be bismuth salt, polyacrylonitrile, dimethyl sulfoxide uniform and stable dispersion, by carbon cloth form a film calcining obtain porous bismuth-carbon composite.Operation of the present invention is simple, consumes energy low, and raw material sources are wide, low in cost, is easily mass produced.Flexibility cathode obtained is not necessarily to outer adding additives, conductive agent and metal collector, and has high carrying capacity, high-capacitance, excellent high rate performance and preferable cyclical stability advantage.
Description
Technical field
The invention belongs to energy storage material technical fields, more particularly, to a kind of preparation side of porous bismuth-carbon composite
Method.
Background technique
The energy is the important foundation resource of human social development.But due to the world energy sources resource place of production and energy-consuming center
It is apart from each other, in particular with the development of world economy, the continuous improvement of the sharp increase of world population and living standards of the people, the world
Demand for energy persistently increases, and thus causes to be growing more intense to the contention of energy resources, environmental pollution exacerbation and environmental protection pressure add
Greatly.Therefore, it is necessary to research and develop energy-storage system efficiently to utilize the energy, and can repeated charge, the adaptation of high-efficient and environment
The strong secondary cell of property is then the important research direction of energy storage technology.
Water system battery is the secondary cell using aqueous solution as electrolyte, and it is high that it overcomes traditional organic system battery electrolyte
Expensive, toxic, inflammable, the disadvantages of ionic conductivity is low, cost of manufacture is high, become most potential after wind energy, solar energy
One of green energy resource.Therefore, water system battery has important application prospect in the extensive energy storage field of power grid rank.With material
The development of material technology, demand of the people to novel high-performance electrode material increasingly improve, and there is an urgent need to high performance by finding
Energy storage material is to improve the performance of water system battery, to meet the needs of industry and life.
Although to the positive electrode of water system battery there are many progress, negative electrode material is seldom studied, and
It is high-performance cathode with development potential since bismuthino material has good electric conductivity and suitable negative potential operation interval
Material.Bismuthino compound is used extensively because its low cost, hypotoxicity, height lead oxygen, good photocatalysis and dielectric properties
Make catalyst, optical material, gas sensor etc..However bismuthino material is seldom in the application study of energy storage field at present, at present
Almost without the application study about bismuth-carbon composite in water system battery.Therefore, develop one kind be simple and efficient, consume energy it is low
Bismuth-carbon composite preparation method and improve the energy-storage property of bismuthino material and be of great significance.
Summary of the invention
The present invention relates to a kind of high carrying capacity, high-capacitance, excellent high rate performance and preferable cyclical stability it is porous
Bismuth-carbon composite preparation method, while being related to composite material and its preparing water system that above-mentioned preparation method is prepared
Application in battery.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of preparation methods of porous bismuth-carbon composite, include the following steps:
S1. polyacrylonitrile is dispersed in dimethyl sulfoxide, bismuth salt is then added, form sol precursor；
S2. carbon cloth is immersed in S1 in sol precursor, heating, drying；
S3. the carbon cloth for passing through heating, drying in S2 is impregnated in potassium hydroxide-ethanol solution, dries, is obtained after calcining more
Hole bismuth-carbon composite；
(50~400) mmol L- is added in every gram of polyacrylonitrile in S11Bismuth salt；Every 10ml dimethyl sulfoxide is added 0.5~
1.5g polyacrylonitrile；The temperature of calcining is 600~800 DEG C, in potassium hydroxide-ethanol solution, the concentration of potassium hydroxide is 0~
6mol L-1。
Preferably, the bismuth salt is five nitric hydrate bismuths.
Preferably, the concentration of potassium hydroxide is 6mol L- in potassium hydroxide-ethanol solution1。
Preferably, 200mmol L- is added in every gram of polyacrylonitrile in S11Bismuth salt；It is poly- that 1g is added in every 10ml dimethyl sulfoxide
Acrylonitrile.
Preferably, calcining is to be fired to 700 DEG C under nitrogen atmosphere and keep the temperature 1 hour in S3.
Preferably, for carbon cloth through over cleaning before using, cleaning method is successively to go from water, ethyl alcohol, acetone, deionized water
Middle ultrasonic cleaning 10 minutes, then 60 DEG C of drying.
The present invention protects obtained porous bismuth-carbon composite of above-mentioned preparation method preparation simultaneously.
The present invention also protects application of the porous bismuth-carbon composite in preparation water system battery.
Further, negative electrode material of the porous bismuth-carbon composite as water system battery.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
Preparation method provided by the invention is easy to operate, and raw material simplicity easily takes, and low in cost, low energy consumption, it is easy to accomplish, system
Standby obtained porous bismuth-carbon composite and flexible negative electrode material is without outer adding additives, conductive agent and metal collector, specific surface area
Height, electric conductivity is excellent, has high capacity and excellent high rate performance, with the negative electrode materials phase such as mature commercial graphite electrode
Than energy-storage property is significantly increased.This material is prepared by simple directly impregnate with the method for calcining, can large area synthesize and wide
It is general to be applied to industrial production, high performance negative electrode material is provided for current water system battery, has great application prospect.
Detailed description of the invention
(a) is high magnification scanning electron microscope (SEM) picture of porous bismuth-carbon composite in embodiment 1 in Fig. 1, (b) is real
Apply porous bismuth in example 1-carbon composite low range scanning electron microscope (SEM) picture.
Fig. 2 is X-ray diffraction (XRD) figure of porous bismuth-carbon composite of embodiment 1.
Fig. 3 is cyclic voltammetry curve of the porous bismuth-carbon composite of embodiment 1 in 6M KOH solution under 100mV/s
(CV)。
Fig. 4 is specific discharge capacity of the porous bismuth-carbon composite of embodiment 1 under different current densities.
Fig. 5 is the cycle life curve of porous bismuth-carbon composite of embodiment 1.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1:
Porous bismuth-carbon composite is realized by high temperature sintering.The step of synthetic method, is as follows:
(a) carbon cloth (2cm × 3cm) is successively going to be cleaned by ultrasonic respectively from water, ethyl alcohol, acetone, deionized water 10 minutes, so
It is dried for standby for 60 DEG C afterwards.
(b) 1g polyacrylonitrile is dispersed with stirring under the conditions of 90 DEG C of oil baths formed in 10mL dimethyl sulfoxide it is colorless and transparent
Colloidal sol is added five nitric hydrate bismuth of 970.1mg (concentration is 200mmol L-1), continues stirring until being formed after being cooled to room temperature
Transparent uniform colloidal sol.
(c) in the colloidal sol by carbon cloth complete wetting prepared by step (b), after carbon cloth is placed on surface plate at 60 DEG C
Drying and natural cooling in baking oven, conductive carbon cloth surfaces form the ganoine thin film of one layer of shallow white uniformity.
(d) carbon cloth that step (c) obtains is impregnated in 30min in the 6mol L-1 potassium hydroxide-ethanol solution of 25mL, so
It is dried in 60 DEG C of baking ovens afterwards, the shallow white uniformity ganoine thin film carbon cloth of carbon cloth surfaces is converted to orange-yellow ganoine thin film；
(e) carbon cloth that step (d) obtains is placed in tube furnace, is fired to 700 DEG C under nitrogen atmosphere and heats 1 hour,
Porous bismuth-the carbon composite of target product is obtained after natural cooling.
Examples 1 to 7 conditional and the results are shown in Table 1:
Table 1: preparation condition and result in Examples 1 to 7
Bismuth-carbon composite energy homoepitaxial in carbon cloth substrate and has porous structure as can be seen from Figure 1, Fig. 2's
XRD curve shows that preparing resulting material only has two kinds of substances of bismuth with elementary and carbon.The CV curve of Fig. 3 shows this porous bismuth-carbon
The redox reaction of high reversible can occur in aqueous KOH solution for combination electrode, can be used as a kind of high performance water system electricity
Pond negative electrode material.Fig. 4 shows that this porous bismuth-carbon composite has very high discharge capacity and excellent high rate performance,
By calculating, the carrying capacity of this porous bismuth-carbon composite is 16.93mgcm-1, electric discharge quality specific capacitance is 91.64mAh g
-1, area specific capacitance is 1.55mAhcm-2, it is shown that its extremely excellent energy storage characteristic.The cycle life curve of Fig. 5 shows this more
Hole bismuth-carbon composite electrode has excellent cyclical stability, and initial capacity can be still kept after 10000 cycle charge-discharges
83%.
Claims (4)
1. a kind of preparation method of porous bismuth-carbon composite, which comprises the steps of:
S1. the carbon cloth of the cm of 2 cm × 3 successively is being gone to be cleaned by ultrasonic respectively 10 minutes from water, ethyl alcohol, acetone, deionized water,
Then it is dried for standby for 60 DEG C；
S2. 1 g polyacrylonitrile is dispersed with stirring under the conditions of 90 DEG C of oil baths formed in 10 mL dimethyl sulfoxides it is colorless and transparent
970.1 mg, five nitric hydrate bismuth is added in colloidal sol after being cooled to room temperature, continue stirring until forming transparent uniform colloidal sol；
S3. by carbon cloth complete wetting in the colloidal sol prepared by step S2, after carbon cloth is placed on surface plate in 60 DEG C of baking
Drying and natural cooling in case, conductive carbon cloth surfaces form the ganoine thin film of one layer of shallow white uniformity；
S4., the step S3 carbon cloth obtained is impregnated in the 6 mol L of 25 mL-130 min in potassium hydroxide-ethanol solution, then
It is dried in 60 DEG C of baking ovens, the shallow white uniformity ganoine thin film carbon cloth of carbon cloth surfaces is converted to orange-yellow ganoine thin film；
S5. the step S4 carbon cloth obtained is placed in tube furnace, is fired to 700 DEG C under nitrogen atmosphere and heats 1 hour, it is natural
Porous bismuth-the carbon composite of target product is obtained after cooling.
2. obtained porous bismuth-carbon composite of preparation method preparation described in claim 1.
3. application of the porous bismuth-carbon composite as claimed in claim 2 in preparation water system battery.
4. application according to claim 3, which is characterized in that the porous bismuth-carbon composite is as water system battery
Negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710227930.4A CN107146915B (en) | 2017-04-10 | 2017-04-10 | A kind of preparation method of porous bismuth-carbon composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710227930.4A CN107146915B (en) | 2017-04-10 | 2017-04-10 | A kind of preparation method of porous bismuth-carbon composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107146915A CN107146915A (en) | 2017-09-08 |
| CN107146915B true CN107146915B (en) | 2019-08-27 |
Family
ID=59774661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710227930.4A Active CN107146915B (en) | 2017-04-10 | 2017-04-10 | A kind of preparation method of porous bismuth-carbon composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107146915B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742327A (en) * | 2018-12-29 | 2019-05-10 | 西安鸿钧睿泽新材料科技有限公司 | Preparation method of self-supporting flexible lithium ion battery carbon cloth loaded LiFePO4 positive electrode material |
| CN109909511B (en) * | 2019-03-22 | 2022-05-03 | 中国工程物理研究院化工材料研究所 | Preparation method and application of bismuth-based hollow nano material |
| CN111477864B (en) * | 2020-04-13 | 2022-02-22 | 山东鲁北国际新材料研究院有限公司 | Preparation method and application of superfine metal bismuth nano material |
| CN112442892B (en) * | 2020-11-02 | 2023-02-28 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under acidic condition |
| CN112349881A (en) * | 2020-11-17 | 2021-02-09 | 河南电池研究院有限公司 | Manufacturing method of flexible current collector-free electrode |
| CN113258025B (en) * | 2021-05-07 | 2023-02-28 | 西北工业大学 | Bismuth-based negative electrode for high-performance water-based battery and preparation method |
| CN113130873B (en) * | 2021-05-20 | 2022-08-12 | 武汉科技大学 | Porous bismuth-carbon material, preparation method and application thereof |
| CN114823153B (en) * | 2022-04-24 | 2023-11-03 | 华星先进科学技术应用研究(天津)有限公司 | Flexible sodium ion capacitor electrode material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522568A (en) * | 2011-12-10 | 2012-06-27 | 中国科学院金属研究所 | Method for preparing electrode material for all-vanadium flow battery |
| CN103545494A (en) * | 2013-10-18 | 2014-01-29 | 南京大学 | Liquid phase synthesis method for submicron bismuth-carbon anode composite for secondary lithium ion batteries |
| CN104241661A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院金属研究所 | Preparation method for combination electrode for all-vanadium redox flow battery |
| CN104518221A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Double-function negative electrode and applications of double-function negative electrode as all-vanadium flow battery negative electrode |
| CN105024056A (en) * | 2015-06-05 | 2015-11-04 | 中南大学 | Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof |
| CN105024050A (en) * | 2015-06-03 | 2015-11-04 | 中南大学 | Bismuth selenide/carbon nanofiber composite anode material for sodium ion battery and preparation method thereof |
| CN106099076A (en) * | 2016-08-22 | 2016-11-09 | 北京化工大学 | A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application |
| CN106252661A (en) * | 2016-10-14 | 2016-12-21 | 成都理工大学 | Bismuth sulfide/carbon nano tube compound material and its preparation method and application |
| CN106299297A (en) * | 2016-09-20 | 2017-01-04 | 华中科技大学 | One is one-dimensional mixes bismuth carbon nanocoils composite and its preparation method and application |
-
2017
- 2017-04-10 CN CN201710227930.4A patent/CN107146915B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522568A (en) * | 2011-12-10 | 2012-06-27 | 中国科学院金属研究所 | Method for preparing electrode material for all-vanadium flow battery |
| CN104518221A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Double-function negative electrode and applications of double-function negative electrode as all-vanadium flow battery negative electrode |
| CN103545494A (en) * | 2013-10-18 | 2014-01-29 | 南京大学 | Liquid phase synthesis method for submicron bismuth-carbon anode composite for secondary lithium ion batteries |
| CN104241661A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院金属研究所 | Preparation method for combination electrode for all-vanadium redox flow battery |
| CN105024050A (en) * | 2015-06-03 | 2015-11-04 | 中南大学 | Bismuth selenide/carbon nanofiber composite anode material for sodium ion battery and preparation method thereof |
| CN105024056A (en) * | 2015-06-05 | 2015-11-04 | 中南大学 | Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof |
| CN106099076A (en) * | 2016-08-22 | 2016-11-09 | 北京化工大学 | A kind of flower-shaped nitrogen-doped carbon cladding bismuth structural composite material and its preparation method and application |
| CN106299297A (en) * | 2016-09-20 | 2017-01-04 | 华中科技大学 | One is one-dimensional mixes bismuth carbon nanocoils composite and its preparation method and application |
| CN106252661A (en) * | 2016-10-14 | 2016-12-21 | 成都理工大学 | Bismuth sulfide/carbon nano tube compound material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107146915A (en) | 2017-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107146915B (en) | A kind of preparation method of porous bismuth-carbon composite | |
| CN107359320B (en) | Nitrogen-doped porous carbon/MoS2Sodium ion battery negative electrode material and preparation method thereof | |
| Cheng et al. | Cu/(Cu (OH) 2-CuO) core/shell nanorods array: in-situ growth and application as an efficient 3D oxygen evolution anode | |
| US11634332B2 (en) | Selenium-doped MXene composite nano-material, and preparation method and use thereof | |
| CN107887592A (en) | Carbon coating ZnO nano-wire and its preparation method and application | |
| CN105780364B (en) | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application | |
| CN105870417B (en) | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite | |
| CN106783203B (en) | A kind of preparation method, product and the application of manganese dioxide/ultramicropore flexibility carbon cloth | |
| CN108855145B (en) | Two-step method for preparing cobalt sulfide/molybdenum sulfide composite material and application of cobalt sulfide/molybdenum sulfide composite material in hydrogen evolution reaction | |
| CN108383098B (en) | Hollow porous carbon material co-doped with various heteroatoms, and preparation method and application thereof | |
| CN103682296B (en) | A kind of preparation method of nanoscale lithium titanate material with high specific capacity | |
| CN109289874B (en) | Cobalt-doped tin disulfide nanosheet array material and preparation method and application thereof | |
| CN103326007A (en) | Preparation method and application of three-dimensional graphene-based stannic oxide composite material | |
| CN110156081A (en) | A kind of porous flake TiNb of negative electrode of lithium ion battery2O7Nanocrystalline preparation method | |
| CN103441246A (en) | Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material | |
| CN109786742B (en) | Se-doped MXene battery negative electrode material and preparation method and application thereof | |
| CN109148859A (en) | A kind of preparation method of double carbon-coating coated manganese oxide composite materials | |
| CN109411739B (en) | Self-generating long-life Zn-CoNC zinc-air battery and application thereof | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| CN106981650B (en) | Preparation method of nanoscale elemental bismuth | |
| CN108987688A (en) | A kind of C-base composte material, preparation method and sodium-ion battery | |
| CN110078130B (en) | Preparation method of hollow-structure iron-based compound and application of hollow-structure iron-based compound as cathode material of supercapacitor | |
| CN108198701A (en) | A kind of cobaltosic oxide/carbon composite electrode material, preparation method and applications | |
| CN106783196B (en) | Preparation method of polyhedral ferric oxide nano material | |
| CN107032414B (en) | A kind of preparation method of flexibility cobalt acid zinc nano-material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |