CN107134572B - A kind of preparation method and application based on nickel phosphide hollow structure composite material - Google Patents
A kind of preparation method and application based on nickel phosphide hollow structure composite material Download PDFInfo
- Publication number
- CN107134572B CN107134572B CN201710348059.3A CN201710348059A CN107134572B CN 107134572 B CN107134572 B CN 107134572B CN 201710348059 A CN201710348059 A CN 201710348059A CN 107134572 B CN107134572 B CN 107134572B
- Authority
- CN
- China
- Prior art keywords
- hollow structure
- composite material
- nickel phosphide
- nickel
- preparation
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
-
- 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
-
- 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 method and applications based on nickel phosphide hollow structure composite material, the method comprises the following steps: (1) prepares Ni- hollow structure material using hydro-thermal reaction；(2) the Ni- hollow structure material after drying is mixed with phosphorus source, is placed in tube furnace and calcines phosphatization, obtain nickel phosphide hollow structure material；(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur, after grinding uniformly, is heated to melting and being subsequently cooled to room temperature, obtained based on nickel phosphide hollow structure composite material.Composite material prepared by the present invention possesses the hollow structure of large scale, to there is apparent confinement to act on sulphur, the shuttle effect of more lithium sulfides is significantly inhibited, furthermore the composite material of high conductivity improves the electrochemical reaction activity of sulphur, and material is made to have taken into account long circulation life and high-energy density.
Description
Technical field
The invention belongs to technical field of energy material, are related to a kind of preparation method and application of composite material, more particularly to
A kind of preparation method and application based on nickel phosphide hollow structure composite material.
Background technique
Lithium-sulfur cell is 5 times of existing lithium ion battery or more since its theoretical specific energy is up to 2600Wh/kg.This
Outside, due to the low cost of sulphur and it is environmental-friendly the features such as, lithium-sulfur cell is by extensive concern and research.But due to lithium sulphur
Use elemental sulfur as anode in battery, and the conductivity of sulphur is very low, furthermore the more lithium sulfides of electric discharge intermediate product of lithium-sulfur cell
It is readily dissolved in ethers electrolyte, so as to cause the loss and the decaying in service life of the capacity of battery entirety.This low electrochemistry is living
Property and short-life intrinsic short slab largely limit the development of lithium-sulfur cell.
In order to overcome the shortcomings of that existing sulphur anode material discharging specific capacity is low, cycle life is poor, people use different lithiums
Sulphur cell positive electrode composite material improves the cycle life of battery to limit the generation of shuttle effect.Recently it has been found that polarity point
Son can be by the effect of polar bond effectively by lithium-sulfur cell electric discharge intermediate product Li2Sn (4≤n≤8) are strapped in electrode surface,
To avoid it from being diffused into lithium piece side.However many polar materials are all electrical isolation substances, to largely reduce
The electro-chemical activity of sulphur anode.Therefore a kind of polar material for possessing high conductivity is needed under the premise of guaranteeing cycle life
Improve the energy density of electrode.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application based on nickel phosphide hollow structure composite material, the party
The composite material of method preparation possesses the hollow structure of large scale, to have apparent confinement to act on sulphur, significantly inhibits more vulcanizations
The shuttle effect of lithium, furthermore the composite material of high conductivity improves the electrochemical reaction activity of sulphur, so that material has been taken into account length and follows
Ring service life and high-energy density.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method based on nickel phosphide hollow structure composite material, includes the following steps:
(1) Ni- hollow structure material is prepared using hydro-thermal reaction: by the nickel salt of 0.5 ~ 5mmol, the alcohol of 100 ~ 300mL, 5 ~
The organic solvent of 15mL, the water of 0.5 ~ 10mL are configured to solution, and are transferred in reaction kettle, carry out water in 90 ~ 200 DEG C of temperature
Thermal response 6 ~ 24 hours, be centrifuged after reaction, ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
In this step, the nickel salt is one of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride；Alcohol is normal propyl alcohol, different
One of propyl alcohol；Organic solvent is one of glycerol, ethylene glycol.
(2) the Ni- hollow structure material after drying is mixed with phosphorus source according to the mass ratio of 1:1 ~ 50, is placed in tube furnace,
Phosphatization is calcined under conditions of 250 ~ 500 DEG C, 1 ~ 12 hour, inert gas shielding, obtains nickel phosphide hollow structure material.
In this step, phosphorus source is one of potassium hypophosphite, sodium hypophosphite, ammonium hypophosphite, red phosphorus, white phosphorus, yellow phosphorus；
Inert gas is one of argon gas, nitrogen, helium.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:0.5 ~ 9,
After grinding uniformly, it is heated to melting under conditions of 120 ~ 250 DEG C, 5 ~ 24 hours, inert gas shielding and is subsequently cooled to room
Temperature is obtained based on nickel phosphide hollow structure composite material.
In this step, the inert gas is one of argon gas, nitrogen, helium.
The invention has the following beneficial effects:
(1) present invention prepares Ni- hollow structure material using hydro-thermal reaction, and passes through phosphating reaction for the hollow knot of the Ni-
Structure material is converted into nickel phosphide hollow structure material, and during inversion of phases, electrode keeps original hollow structure feature.
(2) nickel phosphide hollow structure material is to lithium-sulfur cell electric discharge intermediate product Li2Sn (4≤n≤8) have very strongization
Bonding action is learned, more lithium sulfides are adsorbed by chemical bond in charge and discharge process, to significantly inhibit the generation of shuttle effect.
(3) nickel phosphide hollow structure material has high electric conductivity, is effectively promoted by the recombination energy with sublimed sulfur
The electronic conductivity of compound entirety, to enhance the electro-chemical activity and reaction depth of lithium-sulphur cell positive electrode.
(4) nickel phosphide hollow structure material maintains the high-specific surface area similar to Ni- hollow structure during the preparation process
Property, therefore other than improving electrochemical reaction active interface, additionally it is possible to storage sulphur place abundant is provided, so as to effectively
When lithium-sulfur cell being inhibited to discharge the problem of volume expansion.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photograph of the nickel phosphide hollow structure material prepared by the present invention under the conditions of 50000 times of amplifications；
Fig. 2 is scanning electron microscope (SEM) photograph of the nickel phosphide hollow structure material prepared by the present invention under the conditions of 5000 times of amplifications；
Fig. 3 is the X-ray diffraction spectrogram of nickel phosphide hollow structure material prepared by the present invention；
Fig. 4 be nickel phosphide hollow structure composite material prepared by the present invention as lithium sulfur battery anode material putting in 0.1C
Electric cyclic curve.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1
(1) distilled water of the nickel sulfate of 0.5mmol, the isopropanol of 100mL, the glycerol of 5mL, 0.5mL are configured to first
Solution, and be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 90 DEG C and 6 hours in an oven, reaction terminates gained
To product obtained by way of centrifugation, and using ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
(2) the Ni- hollow structure material after drying is mixed with potassium hypophosphite according to the mass ratio of 1:1, is placed in argon gas gas
In atmosphere tube furnace, phosphatization is calcined under conditions of 250 DEG C, 1 hour, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:0.5, is ground
After mill is uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 120 DEG C, 5 hours, argon gas protection, obtains nickel phosphide
The lithium sulfur battery anode material of hollow structure material.
Embodiment 2
(1) first by the nickel nitrate of 1mmol, the normal propyl alcohol of 300mL, the ethylene glycol of 10mL, 5mL distilled water be configured to it is molten
Liquid, and be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 110 DEG C and 18 hours in an oven, reaction terminates gained
To product obtained by way of centrifugation, and using ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
(2) the Ni- hollow structure material after drying is mixed with ammonium hypophosphite according to the mass ratio of 1:20, is placed in helium gas
In atmosphere tube furnace, phosphatization is calcined under conditions of 400 DEG C, 6 hours, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:4, is ground
After uniformly, it is heated to melting and being subsequently cooled to room temperature under conditions of 200 DEG C, 12 hours, helium protection, obtains nickel phosphide sky
Core structure composite material.
Embodiment 3
(1) first by the nickel acetate of 2mmol, the normal propyl alcohol of 200mL, the glycerol of 15mL, 10mL distilled water be configured to it is molten
Liquid, and be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 140 DEG C and 12 hours in an oven, reaction terminates gained
To product obtained by way of centrifugation, and using ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
(2) the Ni- hollow structure material after drying is mixed with red phosphorus according to the mass ratio of 1:50, is placed in nitrogen atmosphere pipe
In formula furnace, phosphatization is calcined under conditions of 500 DEG C, 12 hours, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:9, is ground
It after uniformly, is heated to melting and being subsequently cooled to room temperature under conditions of 150 DEG C, 18 hours, nitrogen protection, obtains nickel phosphide sky
Core structure composite material.
Embodiment 4
(1) distilled water of the nickel chloride of 4mmol, the isopropanol of 200mL, the glycerol of 5mL, 2mL are configured to solution first,
And be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 200 DEG C and 24 hours in an oven, reaction terminates obtained
Product is obtained by way of centrifugation, and is cleaned using ethyl alcohol, after drying, and Ni- hollow structure material is obtained.
(2) the Ni- hollow structure material after drying is mixed with white phosphorus according to 1:2 mass ratio, is placed in argon atmosphere tubular type
In furnace, phosphatization is calcined under conditions of 300 DEG C, 3 hours, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:1, is ground
After uniformly, it is heated to melting and being subsequently cooled to room temperature under conditions of 250 DEG C, 24 hours, argon gas protection, obtains nickel phosphide sky
Core structure composite material.
Fig. 1 is scanning electron microscope (SEM) photograph of the nickel phosphide hollow structure material manufactured in the present embodiment under the conditions of 50000 times of amplifications
As shown in Figure 1；Scanning electron microscope (SEM) photograph under the conditions of 5000 times of amplifications is as shown in Figure 2；X-ray diffraction spectrogram is as shown in Figure 3.
When the nickel phosphide hollow structure composite material of embodiment preparation is used as lithium sulfur battery anode material, lithium-sulphur cell positive electrode
Discharge cycles curve of the material in 0.1C is as shown in Figure 4.
Embodiment 5
(1) first by the nickel sulfate of 5mmol, the normal propyl alcohol of 300mL, the ethylene glycol of 10mL, 8mL distilled water be configured to it is molten
Liquid, and be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 140 DEG C and 18 hours in an oven, reaction terminates gained
To product obtained by way of centrifugation, and using ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
(2) the Ni- hollow structure material after drying is mixed with sodium hypophosphite according to the mass ratio of 1:10, is placed in nitrogen gas
In atmosphere tube furnace, phosphatization is calcined under conditions of 400 DEG C, 9 hours, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:2, is ground
It after uniformly, is heated to melting and being subsequently cooled to room temperature under conditions of 200 DEG C, 18 hours, nitrogen protection, obtains nickel phosphide sky
Core structure composite material.
Embodiment 6
(1) first by the nickel chloride of 3mmol, the isopropanol of 150mL, the ethylene glycol of 15mL, 8mL distilled water be configured to it is molten
Liquid, and be transferred in reaction kettle, hydro-thermal reaction is carried out under conditions of 110 DEG C and 24 hours in an oven, reaction terminates gained
To product obtained by way of centrifugation, and using ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
(2) the Ni- hollow structure material after drying is mixed with yellow phosphorus according to the mass ratio of 1:5, is placed in helium atmosphere pipe
In formula furnace, phosphatization is calcined under conditions of 500 DEG C, 6 hours, obtains nickel phosphide hollow structure material.
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:7, is ground
After uniformly, it is heated to melting and being subsequently cooled to room temperature under conditions of 120 DEG C, 20 hours, helium protection, obtains nickel phosphide sky
Core structure composite material.
Claims (8)
1. a kind of preparation method based on nickel phosphide hollow structure composite material, it is characterised in that the method comprises the following steps:
(1) Ni- hollow structure material is prepared using hydro-thermal reaction；
(2) the Ni- hollow structure material after drying is mixed with phosphorus source according to the mass ratio of 1:1 ~ 50, is placed in tube furnace, 250
~ 500 DEG C, 1 ~ 12 hour, phosphatization is calcined under conditions of inert gas shielding, obtain nickel phosphide hollow structure material；
(3) the nickel phosphide hollow structure material that step (2) obtain is mixed with sublimed sulfur according to the mass ratio of 1:0.5 ~ 9, is ground
After uniformly, it is heated to melting and being subsequently cooled to room temperature under conditions of 120 ~ 250 DEG C, 5 ~ 24 hours, inert gas shielding, obtains
To based on nickel phosphide hollow structure composite material.
2. the preparation method according to claim 1 based on nickel phosphide hollow structure composite material, it is characterised in that described
Specific step is as follows for step (1):
Ni- hollow structure material prepared using hydro-thermal reaction: by the nickel salt of 0.5 ~ 5mmol, the alcohol of 100 ~ 300mL, 5 ~ 15mL
Organic solvent, 0.5 ~ 10mL water be configured to solution, and be transferred in reaction kettle, carry out hydro-thermal reaction in 90 ~ 200 DEG C of temperature
6 ~ 24 hours, be centrifuged after reaction, ethyl alcohol cleaning, it is dry after, obtain Ni- hollow structure material.
3. the preparation method according to claim 2 based on nickel phosphide hollow structure composite material, it is characterised in that described
Nickel salt is one of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride.
4. the preparation method according to claim 2 based on nickel phosphide hollow structure composite material, it is characterised in that described
Alcohol is one of normal propyl alcohol, isopropanol.
5. the preparation method according to claim 2 based on nickel phosphide hollow structure composite material, it is characterised in that described
Organic solvent is one of glycerol, ethylene glycol.
6. the preparation method according to claim 1 based on nickel phosphide hollow structure composite material, it is characterised in that described
Phosphorus source is one of potassium hypophosphite, sodium hypophosphite, ammonium hypophosphite, red phosphorus, white phosphorus, yellow phosphorus.
7. the preparation method according to claim 1 based on nickel phosphide hollow structure composite material, it is characterised in that described
Inert gas is one of argon gas, nitrogen, helium.
8. a kind of preparation of claim 1-7 any claim the method based on nickel phosphide hollow structure composite material in lithium
Application in sulphur cell positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348059.3A CN107134572B (en) | 2017-05-17 | 2017-05-17 | A kind of preparation method and application based on nickel phosphide hollow structure composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710348059.3A CN107134572B (en) | 2017-05-17 | 2017-05-17 | A kind of preparation method and application based on nickel phosphide hollow structure composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107134572A CN107134572A (en) | 2017-09-05 |
| CN107134572B true CN107134572B (en) | 2019-04-30 |
Family
ID=59732388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710348059.3A Expired - Fee Related CN107134572B (en) | 2017-05-17 | 2017-05-17 | A kind of preparation method and application based on nickel phosphide hollow structure composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107134572B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107665984B (en) * | 2017-09-13 | 2020-01-14 | 哈尔滨工业大学 | Preparation method of lithium-sulfur battery positive electrode material based on phosphorus-doped graphene-loaded nickel phosphide material |
| CN107952458A (en) * | 2017-11-02 | 2018-04-24 | 天津大学 | Preparation method applied to the nickel phosphorus catalyst of efficient electric catalyzing manufacturing of hydrogen |
| CN108493426A (en) * | 2018-04-13 | 2018-09-04 | 西北大学 | A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery |
| CN109055975A (en) * | 2018-08-01 | 2018-12-21 | 北京工业大学 | One kind preparing porous Ni based on two-dimensional metallic organic backbone template2The method of P/C electrode |
| CN110707321A (en) * | 2019-10-23 | 2020-01-17 | 合肥国轩高科动力能源有限公司 | Copper-coated hollow nickel phosphide material and preparation method and application thereof |
| CN112604717A (en) * | 2020-12-29 | 2021-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of quantum dot iron-based metal organic framework composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150451A (en) * | 2014-08-06 | 2014-11-19 | 陕西科技大学 | Preparation method for nickel phosphide with hollow core-shell structure |
| CN105148958A (en) * | 2015-09-21 | 2015-12-16 | 天津工业大学 | Synthetic method of sulfur-doped iron phosphide hydrodesulfurization catalyst |
| CN105609720A (en) * | 2015-12-29 | 2016-05-25 | 哈尔滨工业大学 | Preparation method and application of NiPC@CNTs/S composite material |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10236135B2 (en) * | 2015-06-25 | 2019-03-19 | William Marsh Rice University | Ni(OH)2 nanoporous films as electrodes |
-
2017
- 2017-05-17 CN CN201710348059.3A patent/CN107134572B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150451A (en) * | 2014-08-06 | 2014-11-19 | 陕西科技大学 | Preparation method for nickel phosphide with hollow core-shell structure |
| CN105148958A (en) * | 2015-09-21 | 2015-12-16 | 天津工业大学 | Synthetic method of sulfur-doped iron phosphide hydrodesulfurization catalyst |
| CN105609720A (en) * | 2015-12-29 | 2016-05-25 | 哈尔滨工业大学 | Preparation method and application of NiPC@CNTs/S composite material |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Template-free synthesis of Ni2P hollow microspheres with great photocatalytic and electrochemical properties";Shuling Liu et al.;《Journal of Materials Science:Materials in Electronics》;20151111;第27卷;全文 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107134572A (en) | 2017-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107134572B (en) | A kind of preparation method and application based on nickel phosphide hollow structure composite material | |
| US10770720B2 (en) | Composite negative electrode material and method for preparing composite negative electrode material, negative electrode plate of lithium ion secondary battery, and lithium ion secondary battery | |
| CN106654221B (en) | Three-dimensional porous carbon coating selenizing Zinc material and preparation method thereof for negative electrode of lithium ion battery | |
| CN106532012B (en) | A kind of sulphur-biomass carbon/transition metal combination electrode material and its preparation method and application | |
| CN105655555B (en) | A kind of Si-C composite material, preparation method and applications | |
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN106876686B (en) | Method for surface modification of positive electrode active material for lithium ion battery | |
| CN107123810B (en) | A kind of preparation method and applications based on nickel phosphide skeleton structure composite material | |
| CN104134783B (en) | Nano nickel sulphide/grapheme composite positive electrode material and preparation method thereof | |
| CN106505194A (en) | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN110729470B (en) | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application | |
| CN102324511A (en) | Preparation method for lithium ion battery composite cathode material | |
| CN109671929A (en) | The Li-Si alloy composite negative pole material and preparation method thereof of sulfide electrolyte cladding | |
| CN107068964A (en) | Lithium aluminum alloy surface modified lithium cathode and solid-state battery thereof | |
| CN107732180A (en) | A kind of preparation method for water system sodium-ion battery anode composite material | |
| CN102130359A (en) | Lithium sulfur battery and preparation method thereof | |
| CN109473647A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN105762441B (en) | The preparation method of lithium-air battery based on lithium ion solid electrolyte | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN111653734A (en) | Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof | |
| CN108649181A (en) | A kind of no dendrite high circulation service life potassium metal electrode and its preparation method and application | |
| CN107492659A (en) | Aluminium-sulfur battery and its preparation method and application | |
| CN106450203A (en) | Preparation method of metallic oxide/conducting polymer dually-modified sulfur composite anode material | |
| CN103395846A (en) | Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |