CN106784660B - Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof - Google Patents
Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof Download PDFInfo
- Publication number
- CN106784660B CN106784660B CN201611092222.6A CN201611092222A CN106784660B CN 106784660 B CN106784660 B CN 106784660B CN 201611092222 A CN201611092222 A CN 201611092222A CN 106784660 B CN106784660 B CN 106784660B
- Authority
- CN
- China
- Prior art keywords
- tio
- nff
- interlayer
- nanofiber
- secondary cell
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-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
- H01M4/38—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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of Se-TiO of nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof, belongs to technical field of lithium ion.It is that vinylpyrrolidone is dissolved in ethyl alcohol, adds glacial acetic acid and butyl titanate, stirs to get spinning solution;Spinning product is pre-oxidized, obtains TiO by then spinning under high voltage2Nanofiber;2~8h is ground with after the mixing of Se particle, 6~12h is roasted after tabletting under the conditions of argon gas, 200~260 DEG C, obtains Se-TiO2Nanofiber;It is mixed with conductive agent, binder, gained slurry is coated on aluminium foil, obtains Se-TiO2Positive electrode;In Se-TiO2NFF interlayer is added between positive electrode and diaphragm, lithium piece is used as to electrode assembling half-cell, to obtain Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of Se-TiO of nickel foam as interlayer2/NFF
Lithium selenium secondary cell and preparation method thereof.
Background technique
High-energy density, long circulation life and low cost are the developing direction of batteries of electric automobile.Lithium-sulfur cell is because having
Very high Theoretical Mass specific energy (2567Wh/kg), volume and capacity ratio (3467mAh/cm3) and low cost be considered as most answering
With one of the next-generation high-specific energy battery system of prospect.But the lower high rate performance for leading to battery of the electric conductivity of sulphur is not high,
And more sulphions dissolve in ethers electrolyte and cause shuttle effect, cause the stable circulation performance of battery poor.For many years,
People such as consolidate the modification on sulphur, electrolyte and diaphragm by various effort, improve the electrification of lithium-sulfur cell to a certain extent
Performance is learned, but itself insulating properties of its essential problem such as sulphur is not resolved.
Selenium and sulphur are located at same main group in the periodic table of elements, and selenium is expected to the substitute as lithium-sulfur cell future.Although
The specific discharge capacity of selenium (675mAh/g) is lower than sulphur (1672mAh/g), but on volume and capacity ratio selenium (3253mAh/cm) with
Quite, due to receiving the limitation in battery pack space, volume and capacity ratio is more important with specific discharge capacity for sulphur (3467mAh/cm).
The electronic conductivity (1 × 10 of selenium-3S/m) than sulphur (5 × 10-28S/m) much higher, it means that active material in electrode material
Load capacity is expected to much higher than sulfur-based positive electrode, and selenium has a higher utilization rate than sulphur, better electro-chemical activity, quickly with lithium ion
It reacts, to realize higher practical specific energy.Therefore, selenium is expected to become the anode for being specifically applied to building high-energy battery
Material, including domestic electronic appliances and means of transport.
However, selenium equally can also undergo decaying and the coulombic efficiency of the capacity as caused by the dissolution of more selenides as sulphur
Reduction.In order to improve the performance of battery, people take many measures, and a kind of strategy is the selenium material of synthesis different shape structure
Material, such as the nanoporous or nano-fiber material of selenium.Another strategy is selenium to be fixed in porous matrix to pass through suction
It receives material and chases more selenides.It is worn in addition, also increasing by a layer interlayer between electrode slice and diaphragm equally and can also play inhibition
The effect of shuttle effect.
The present invention uses nickel foam (NFF) to be placed in electrode slice and diaphragm as interlayer for the first time, and uses TiO2As
The matrix of lithium selenium cell obtains cycle performance and all good lithium selenium secondary cell of high rate performance.
Summary of the invention
Se- the purpose of the present invention is to provide a kind of simply a kind of nickel foam of novel preparation process as interlayer
TiO2/ NFF lithium selenium secondary cell and preparation method thereof, its step are as follows for the preparation method:
1) TiO is prepared2Nanofiber
0.2~0.4g vinylpyrrolidone is dissolved in 6~8mL ethyl alcohol, adds 2~4mL glacial acetic acid and 1~5mL metatitanic acid
Four butyl esters, stirring 12~obtain spinning solution for 24 hours;Then the spinning under the high voltage of 15~20KV, then by spinning product 400
6~12h is pre-oxidized under the conditions of~700 DEG C, obtains the TiO of 80~100nm of diameter2Nanofiber;
2) Se-TiO is prepared2Positive electrode
The TiO that step 1) is prepared2Nanofiber and Se particle grind 2~8h, tabletting after mixing with mass ratio 1:1
6~12h is roasted under the conditions of argon gas, 200~260 DEG C afterwards, Se particle is made to enter TiO2Nanofiber it is mesoporous in, obtain
Se-TiO2Nanofiber;By Se-TiO obtained2Nanofiber, conductive agent (super P, conductive black), binder (SA, sea
Mosanom) it is mixed according to the ratio of mass ratio 8:1:1, gained slurry is coated on aluminium foil, obtains Se-TiO2Positive electrode;
3) Se-TiO is prepared2/ NFF lithium selenium secondary cell
By nickel foam tabletting at 10~20 μm of thickness of disk, carried out with 2M salt acid elution, then with deionized water and ethyl alcohol
It rinses, obtains NFF interlayer:
In Se-TiO2NFF interlayer is added between positive electrode and diaphragm (Celgard 2300), lithium piece is used as to electrode group
Half-cell is filled, to obtain Se-TiO of the nickel foam of the present invention as interlayer2/ NFF lithium selenium secondary cell.
A kind of Se-TiO of the nickel foam of the present invention as interlayer2/ NFF lithium selenium secondary cell, it is characterised in that be
It is prepared by the above method.
The beneficial effects of the present invention are:
(1) Se-TiO prepared2Nanofiber pattern is uniform, purity is high, reproducible.
(2) raw material that preparation uses are cheap and easy to get, at low cost, are not necessarily to expensive device.
(3) simple process, favorable reproducibility can be not only used for experimental implementation, and can industrially be mass produced.
(4) anode material for lithium-ion batteries Se-TiO prepared by the present invention2/ NFF capacity with higher, stable circulation
High rate performance.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the present invention and its performance of material is prepared, correlation is given below
Diagram.
Fig. 1 is NFF interlayer and Se/TiO prepared by embodiment 12The scanning electron microscope (SEM) photograph (SEM) of nanofiber.Scheming (a) is 40
The scanning electron microscope (SEM) photograph (SEM) of NFF under μm scale, it can be seen that NFF is hole configurations.Scheming (b) is Se/TiO under 1 μm of scale2It receives
The scanning electron microscope (SEM) photograph (SEM) of rice fiber, it can be clearly seen that Se/TiO2The diameter of nanofiber about 100~120nm, it is whole
Even thickness, soilless sticking.
Fig. 2 is X-ray diffraction (XRD) map that embodiment 1 prepares material.Wherein curve 3 is the Se/TiO of preparation2It receives
The map of rice fiber, curve 1 and curve 2 are respectively Se and TiO2XRD spectrum.Comparison show that the x- of prepared material is penetrated
The map free from admixture peak line diffraction (XRD) occurs, that is, proves that the material of preparation is the Se-TiO of pure phase2。
Fig. 3 is Se-TiO prepared by embodiment 12As positive electrode, NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, and the CV of the half-cell of production schemes, in first lap discharge process, Se quilt
More selenides are reduced into, more selenides are further reduced into Li2The process of Se has a wider oxidation peak at 2.3V, right
Answer Li2Transformation of the Se to more selenides and Se.There are two pairs of new redox peaks simultaneously, wherein 1.7V/2.0V is TiO2
The peak of offer;And 1.4V/1.9V is to produce the peak of new redox reaction, that is, the Li generated2Se has occurred reversible with nickel
Redox reaction generate Ni3Se2, 1.9V corresponds to Li2Se to Ni3Se2Transformation, 1.4V corresponds to Ni3Se2To Li2Se
Transformation.This new redox reaction restrained effectively the loss of capacity, improve the performance of battery.
Fig. 4 is Se-TiO prepared by embodiment 12As positive electrode, NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the cycle performance figure of the half-cell of production.There are 2 curves, curve in figure
1 represents coulombic efficiency, and curve 2 represents specific discharge capacity.It is seen that under 0.5C (337.5mAh/g) current density,
After 200 circulations, specific discharge capacity holding still can achieve 597mAh/g, and coulombic efficiency shows material close to 100%
Material has preferable cyclical stability.
Fig. 5 is Se-TiO prepared by embodiment 12As positive electrode, NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the big circulation performance map of the half-cell of production.There are 2 songs in figure
Line, curve 1 represent coulombic efficiency, and curve 2 represents specific discharge capacity.It can be seen from the figure that in the big of 30C (20250mA/g)
Under current density charge-discharge test, being recycled by 500 times, the specific discharge capacity capacity of material remains to be maintained at 178mAh/g, and
And coulombic efficiency illustrates that material has preferable cyclical stability and excellent high rate during charging-discharging close to 100%.
Fig. 6 is Se-TiO prepared by embodiment 12As positive electrode, NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the half-cell of production respectively 0.5C, 1C, 2C, 5C, 10C, 20C,
Discharge test high rate performance figure under 30C difference current density.It can be seen from the figure that material is under the test of each current density
Stable circulation, and under the high current of 30C, the specific capacity of material still can achieve 303mAh/g, it was demonstrated that material have compared with
Outstanding high rate performance.
Fig. 7 is Se-TiO prepared by embodiment 22As positive electrode, NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the cycle performance figure of the half-cell of production.There are two curves in figure, it is bent
Line 1 is Se-TiO2/ NFF material, curve 2 are Se-TiO2Material.Curve 2 is as a comparison.It is seen that curve 2
Under 0.5C (337.5mAh/g) current density, after 100 circulations, specific discharge capacity is only 124mAh/g, and curve 1
It still can achieve 597mAh/g through 100 circulation specific discharge capacities.It illustrates that NFF interlayer can absorb more selenides, inhibits to hold
The loss of amount.
Fig. 8 is the Se of the preparation of embodiment 3 as positive electrode, and NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the cycle performance figure of the half-cell of production.There are two curves in figure, it is bent
Line 1 is Se-TiO2/ NFF material, curve 2 are Se/NFF material.Curve 2 is as a comparison.It is seen that curve 2 exists
Under 0.5C (337.5mAh/g) current density, after 100 circulations, specific discharge capacity only remains 152mAh/g, and curve 1
It still can achieve 597mAh/g through 100 circulation specific discharge capacities.Illustrate TiO2It can play the role of solid selenium, to inhibit
Shuttle effect.
Fig. 9 is the Se of the preparation of embodiment 4 as positive electrode, and NFF is placed in positive electrode and diaphragm as interlayer
Between (Celgard 2300), lithium piece is used as to electrode, the cycle performance figure of the half-cell of production.There are two curves in figure, it is bent
Line 1 is Se-TiO2/ NFF material, curve 2 are Se material.Curve 2 is as a comparison.It is seen that curve 2 is in 0.5C
Under (337.5mAh/g) current density, after 100 circulations, specific discharge capacity only remains 38mAh/g, and curve 1 is through 100
Secondary circulation specific discharge capacity still can achieve 597mAh/g.Illustrate TiO2It can play the role of solid selenium, NFF interlayer can be inhaled
More selenides are received, the two is the shuttle effect in mutual collaboration inhibition lithium selenium cell, and then improves the chemical property of battery.
Specific embodiment
Embodiment 1:
1) 0.35g vinylpyrrolidone is dissolved in 6.5mL ethyl alcohol, adds 2mL glacial acetic acid and 1.5mL butyl titanate, stirs
12h is mixed as spinning solution, spinning solution is sucked and is fixed on syringe with clip upper in manifold with the syringe of 10mL
End, it is to receive material that aluminium foil is placed in the underface of syringe, and the distance controlling from syringe tip to aluminium foil is in 20cm or so, so
The spinning under the high voltage of about 18KV afterwards obtains white filiform and is laid in aluminium foil surface.Obtained white filiform is taken out,
10h pre-oxidation, as TiO are carried out at 550 DEG C2Nanofiber.The TiO that will be prepared2Nanofiber and Se particle are with mass ratio
1:1 grinds 5h, and tabletting is placed in the reaction kettle full of argon gas, and 260 DEG C of roasting 10h make Se enter TiO2It is mesoporous in, obtain
Se-TiO2Nanofiber.The Se-TiO that will be obtained2Material, conductive agent (super P, i.e. conductive black), binder (SA, i.e. sea
Mosanom) it is mixed according to mass ratio 8:1:1, gained slurry is coated on aluminium foil (thickness of slurry is 0.02mm), is placed in 120 DEG C
Vacuum drying oven 10h, obtains Se-TiO2Electrode material.It will be cut into the disk of diameter 12mm thickness 20um after nickel foam tabletting, uses 2M
Salt acid elution, then be rinsed with deionized water and ethyl alcohol.With Se-TiO2As positive electrode, assembled battery is being full of argon gas
Glove box in carry out, with Se-TiO2For positive electrode, NFF is placed in positive electrode and diaphragm (Celgard as interlayer
It 2300) is to electrode with lithium piece, electrolyte is bis- (chloroform) the sulfimide lithium salts of 1mol/L and 1,2- dimethoxy between
Ethane and 1,3- dioxy are defended the mixed solution that ring is formed with volume ratio 1:1, are packaged, and nickel foam of the present invention has been obtained
Se-TiO as interlayer2/ NFF secondary cell.
The cycle performance of battery curve of preparation is respectively as shown in figure 4, charging and discharging currents density is 0.5C.Big circulation
Energy curve is as shown in figure 5, charging and discharging currents density is 30C, it can be seen that the cycle performance of battery is preferable.High rate performance figure is as schemed
Shown in 6, charging and discharging currents density is 0.5C, 1C, 2C, 5C, 10C, 20C, 30C, shows that battery has preferable high rate performance.
Raw material described in this example can be bought from commercial channel.
Embodiment 2:
It is not adding NFF interlayer in assembled battery in place of the difference of embodiment 2 and embodiment 1, due to not having interlayer
More selenides are absorbed, electrochemical cycle stability and high rate performance are relatively low, see Fig. 7.
Embodiment 3:
It is not prepare TiO in place of the difference of embodiment 3 and embodiment 12Nanofiber, that is, it is directly that Se is mono-
Matter and SP, SA smear are made into electrode material, and NFF interlayer is added in when assembled battery, due to not having TiO2Gu selenium, electrochemistry circulation is steady
Qualitative and high rate performance is relatively low, sees Fig. 8.
Embodiment 4:
It is to use Se simple substance direct smear in place of the difference of embodiment 4 and embodiment 1, and does not also have in assembled battery
NFF interlayer is added, due to not only not consolidating selenium, but also does not have the more selenides of interlayer absorption, electrochemical cycle stability and high rate performance are minimum,
See Fig. 9.
Claims (3)
1. a kind of Se-TiO of nickel foam as interlayer2The preparation method of/NFF lithium selenium secondary cell, its step are as follows:
1) TiO is prepared2Nanofiber
0.2~0.4g vinylpyrrolidone is dissolved in 6~8mL ethyl alcohol, adds four fourth of 2~4mL glacial acetic acid and 1~5mL metatitanic acid
Ester, stirring 12~obtain spinning solution for 24 hours;Then the spinning under the high voltage of 15~20KV, then by spinning product 400~
6~12h is pre-oxidized under the conditions of 700 DEG C, obtains the TiO of 80~100nm of diameter2Nanofiber;
2) Se-TiO is prepared2Positive electrode
The TiO that step 1) is prepared2Nanofiber and Se particle grind 2~8h after mixing with mass ratio 1:1, after tabletting
Argon gas roasts 6~12h under the conditions of 200~260 DEG C, and Se particle is made to enter TiO2Nanofiber it is mesoporous in, obtain Se-TiO2
Nanofiber;By Se-TiO obtained2Nanofiber, conductive agent, binder are mixed according to the ratio of mass ratio 8:1:1, gained
Slurry is coated on aluminium foil, obtains Se-TiO2Positive electrode;
3) Se-TiO is prepared2/ NFF lithium selenium secondary cell
By nickel foam tabletting at 10~20 μm of thickness of disk, it is rinsed with 2M salt acid elution, then with deionized water and ethyl alcohol,
Obtain NFF interlayer;In Se-TiO2NFF interlayer is added between positive electrode and diaphragm, lithium piece is used as to electrode assembling half-cell,
To obtain Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell.
2. a kind of Se-TiO of the nickel foam as described in claim 1 as interlayer2The preparation method of/NFF lithium selenium secondary cell,
It is characterized by: the conductive agent is conductive black, the binder is sodium alginate.
3. a kind of Se-TiO of nickel foam as interlayer2/ NFF lithium selenium secondary cell, it is characterised in that: be by claims 1 or 2
The method is prepared.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611092222.6A CN106784660B (en) | 2016-12-02 | 2016-12-02 | Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611092222.6A CN106784660B (en) | 2016-12-02 | 2016-12-02 | Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106784660A CN106784660A (en) | 2017-05-31 |
CN106784660B true CN106784660B (en) | 2019-04-05 |
Family
ID=58915719
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611092222.6A Expired - Fee Related CN106784660B (en) | 2016-12-02 | 2016-12-02 | Se-TiO of the nickel foam as interlayer2/ NFF lithium selenium secondary cell and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106784660B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111180711B (en) * | 2020-01-22 | 2022-11-22 | 河北大学 | Preparation method of graphene-coated oxide-selenium composite aluminum battery positive electrode material |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102623678A (en) * | 2012-03-22 | 2012-08-01 | 华中科技大学 | Preparation method of anode material of Li-Se battery and lithium battery |
CN103178246A (en) * | 2013-03-04 | 2013-06-26 | 中国科学院化学研究所 | Selenium-mesoporous carrier compound, as well as preparation method and application thereof |
CN103187559A (en) * | 2013-03-04 | 2013-07-03 | 中国科学院化学研究所 | Selenium-micropore carrier composite, preparation method and application thereof |
CN104157860A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院化学研究所 | Sodium-selenium cell and preparation method thereof |
CN104393304A (en) * | 2014-11-13 | 2015-03-04 | 清华大学深圳研究生院 | Lithium-selenium battery positive electrode material, preparation method thereof and lithium-selenium battery |
CN104733677A (en) * | 2015-03-25 | 2015-06-24 | 中国科学院化学研究所 | Lithium-selenium battery and preparation technology thereof |
CN105957723A (en) * | 2016-05-31 | 2016-09-21 | 浙江大学 | Method for preparing cobaltous selenide super-capacitor material through chemical vapor deposition method |
CN106024405A (en) * | 2016-05-31 | 2016-10-12 | 浙江大学 | Method for preparing cobalt selenide super-capacitor material by non-template electrodeposition method |
-
2016
- 2016-12-02 CN CN201611092222.6A patent/CN106784660B/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102623678A (en) * | 2012-03-22 | 2012-08-01 | 华中科技大学 | Preparation method of anode material of Li-Se battery and lithium battery |
CN103178246A (en) * | 2013-03-04 | 2013-06-26 | 中国科学院化学研究所 | Selenium-mesoporous carrier compound, as well as preparation method and application thereof |
CN103187559A (en) * | 2013-03-04 | 2013-07-03 | 中国科学院化学研究所 | Selenium-micropore carrier composite, preparation method and application thereof |
CN104157860A (en) * | 2013-05-13 | 2014-11-19 | 中国科学院化学研究所 | Sodium-selenium cell and preparation method thereof |
CN104393304A (en) * | 2014-11-13 | 2015-03-04 | 清华大学深圳研究生院 | Lithium-selenium battery positive electrode material, preparation method thereof and lithium-selenium battery |
CN104733677A (en) * | 2015-03-25 | 2015-06-24 | 中国科学院化学研究所 | Lithium-selenium battery and preparation technology thereof |
CN105957723A (en) * | 2016-05-31 | 2016-09-21 | 浙江大学 | Method for preparing cobaltous selenide super-capacitor material through chemical vapor deposition method |
CN106024405A (en) * | 2016-05-31 | 2016-10-12 | 浙江大学 | Method for preparing cobalt selenide super-capacitor material by non-template electrodeposition method |
Also Published As
Publication number | Publication date |
---|---|
CN106784660A (en) | 2017-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102738458B (en) | Surface modification method of lithium-rich cathode material | |
CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
CN109742360B (en) | Preparation method of high-capacity molybdenum selenide-chlorella derived carbon-less-layer composite battery anode material | |
He et al. | Solvent-free mechanochemical synthesis of Na-rich Prussian white cathodes for high-performance Na-ion batteries | |
CN103441259B (en) | A kind of high magnification aquo-base metal electrochemical cells positive electrode and preparation method thereof | |
CN102903973B (en) | Battery | |
CN105958131A (en) | Rechargeable water system zinc ion battery with long cycle life and high energy density | |
Lou et al. | Facile fabrication of interconnected-mesoporous T-Nb2O5 nanofibers as anodes for lithium-ion batteries | |
CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
CN103346317B (en) | Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof | |
CN108598394B (en) | Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof | |
CN108011105A (en) | Carbon nanosheet material, preparation thereof and application thereof in sodium-ion battery | |
CN109767928B (en) | Synthetic method and application of fluorine-doped carbon-coated silicon oxide nanoparticle @ carbon nanotube composite material | |
CN102633300A (en) | Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof | |
CN103094583B (en) | The processing method of battery and battery afflux liquid | |
CN110335764B (en) | Pre-sodium treatment method for efficiently constructing sodium ion capacitor | |
CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
CN106340633A (en) | Composite nano material for high performance lithium ion battery and preparation method thereof | |
CN103606672A (en) | Rod-shaped nano iron oxide electrode material, and preparation method and application thereof | |
CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
CN106935830A (en) | A kind of lithium ion battery composite cathode material and its preparation method and application | |
CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
CN104282883A (en) | Composite anode material for lithium ion battery, negative plate of lithium ion battery and lithium ion battery | |
CN110336035B (en) | Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof | |
CN110676447B (en) | High-voltage workable composite anode and preparation method thereof |
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: 20190405 Termination date: 20211202 |
|
CF01 | Termination of patent right due to non-payment of annual fee |