CN106784815A - A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery - Google Patents
A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery Download PDFInfo
- Publication number
- CN106784815A CN106784815A CN201611201709.3A CN201611201709A CN106784815A CN 106784815 A CN106784815 A CN 106784815A CN 201611201709 A CN201611201709 A CN 201611201709A CN 106784815 A CN106784815 A CN 106784815A
- Authority
- CN
- China
- Prior art keywords
- iron
- electrode material
- preparation
- sulfide
- sulfide electrode
- 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.)
- Granted
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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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 provides a kind of iron-based sulfide electrode material, preparation method and the application in solid state battery, belong to lithium secondary battery technical field.Iron-based sulfide electrode material based on conversion reaction is selected from one or more of ferrous sulfide, ferriferrous sulfide and eight seven iron of vulcanization.The preparation method of this iron-based sulfide electrode material has simple timesaving advantage.
Description
Technical field
The invention belongs to lithium secondary battery technical field, be related to a kind of iron-based sulfide electrode material, preparation method and its
Application in solid state battery.
Background technology
Lithium ion battery due to having the advantages that energy density is high, discharge voltage is high, having extended cycle life and memory-less effect,
It is widely used in the field such as consumer electronics and communication, it is following to have in hybrid-electric car and scale energy storage field
There is vast potential for future development.But, conventional lithium ion battery, as lithium ion conducting medium, is existed generally using organic electrolyte
The safety issue such as inflammable, perishable and heat endurance is poor so that the application of lithium ion battery is restricted.Meanwhile, lithium metal
A series of side reaction can occur with liquid electrolyte in liquid state batteries, such as metallic lithium surface directly contact electrolyte can be sent out
Biochemical hair is answered, and generates one layer of uneven solid electrolyte film in metallic lithium surface.And due to electricity in charge and discharge process
Current density skewness, can cause the solid electrolyte film of metallic lithium surface crackle or even situation about coming off, lithium metal occur
Negative pole constantly dissolves.Additionally, the growth of Li dendrite can cause barrier film to pierce through, ultimately result in battery short circuit and fail.
Solid state battery is using organic in inorganic solid electrolyte or polymer dielectric substitution conventional lithium ion battery
Electrolyte, with security performance and thermal stability higher, it is considered to be thoroughly solve the problems, such as lithium ion battery security
Ultimate scheme.The inorganic solid electrolyte of current most study includes sulfide solid electrolyte and solid oxide electrolyte two
Major class.Inorganic solid electrolyte material has conductivity at room temperature and mechanical strength higher, and electrochemical window is wide, thermally-stabilised
Property is good.And copolymer solid electrolyte is mainly the material system with PEO as matrix.The High temperature ion of this kind of material
Electrical conductivity is higher, and easy film forming, machining property is good.The solid lithium battery security performance being made of solid electrolyte is obvious
Better than liquid state batteries, the danger of leakage, burning and blast that organic electrolyte occurs in use is efficiently solved.It is another
Aspect, solid electrolyte mechanical strength high can effectively suppress the growth of Li dendrite, and not have interface side reaction, cyclical stability
It is significantly improved with security performance.Also make it possible that lithium metal is applied in battery as negative material, enters one simultaneously
Step improves the energy density of battery.
Now widely used positive electrode is generally lithium-containing transition metal oxide and phosphate electrode (LiCoO2,
LiMn2O4, LiNiO2, LiFePO4), this kind of material has operating voltage and cyclical stability high, but theoretical specific capacity is logical
Often it is relatively low, improve battery energy density it is limited in one's ability.Sulfenyl and transient metal sulfide electrode although operating voltage is relatively low,
But its theoretical specific capacity is very high, the energy density of battery is favorably improved.In solid state battery, how to reduce interface resistance is to carry
Circulating battery stability high, gives full play to the key point of positive electrode capacity.Existed as positive electrode using transient metal sulfide
Significantly Volume Changes are generally entailed in charge and discharge process, this may result in electrode efflorescence or electrode contacts boundary with electrolyte
There is the situation of loose contact in face.Microscopic appearance can be alleviated in cyclic process for the transient metal sulfide electrode material of sheet
Internal stress, suppress Volume Changes effect caused by electrode structure destruction.Meanwhile, two-dimensional sheet structure has larger ratio
Surface area, by increasing capacitance it is possible to increase electrode and the contact area of solid electrolyte, reduces interface contact resistance, increases the work of electrochemical reaction
Property site.Thin nanometer sheet also contributes to shorten the transmission range of lithium ion and electronics, improves electrochemical reaction dynamics.
Iron-based sulfide electrode because raw material is cheap and rich reserves, while environment-friendly, specific capacity is high with good
Research Prospects.At present, generally using complex process and time-consuming solvent heat and hydro-thermal method mistake of the synthesis with certain microscopic appearance
Cross metal sulfide electrode material.Therefore, develop simple timesaving synthetic method and obtain the iron-based sulfide with specific morphology
Electrode material is most important.
The content of the invention
The invention provides a kind of iron-based sulfide electrode material, this iron-based sulfide electrode material can improve solid state battery
Chemical property, be on the one hand due to iron-based sulfide have theoretical specific capacity and moderate operating voltage higher, application
The energy density of solid state battery can be improved in solid state lithium battery；Iron-based sulfide electrode material is micro- in another aspect the application
Sight pattern is two-dimensional sheet structure, by increasing capacitance it is possible to increase electrode and the contact area of solid electrolyte, reduces interface contact resistance, while
Nanometer chip architecture can effectively shorten lithium ion transport distance, electrochemical reaction dynamics be improved, so as to improve solid state battery
Chemical property.Therefore, the iron-based sulfide electrode material that prepared by the application has preferable cycle performance.
The present invention provides a kind of preparation method of iron-based sulfide electrode material again, the iron-based sulfide electricity that the application is provided
Pole material preparation method can improve the performance of solid state battery, specifically, the active material by synthesizing two-dimensional sheet, increase its with
The contact area of electrolyte and conductive additive, alleviates the volume effect in cyclic process while reducing interface contact resistance
Should, the final energy density and cyclical stability for improving solid state battery.
This application provides a kind of preparation method of iron-based sulfide electrode material, comprise the following steps：
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirring obtains mixed solution；In inert atmosphere protection
Under, above-mentioned mixed solution sodium sulfide solution is stirred and is mixed, black precipitate is obtained after reaction.
B) will be dried after black precipitate centrifuge washing, obtain last iron-based sulfide electrode material.
Preferably, the aqueous solution of the preparing raw material, the concentration of ferrous salt is 1wt%~80wt%；Polyvinyl alcohol is water-soluble
The concentration of liquid is 0.01wt%~30%；The concentration of aqueous sodium persulfate solution is 1wt%~80wt%.
Preferably, the mixing temperature is 0~100 DEG C, and the mixing time is 0.001~10h.
Preferably, the dry selection freeze-drying or 80 DEG C of vacuum drying, the drying time is 12~36h.
Preferably, the ferrous salt of the selection is FeSO4·7H2O and FeCl2·4H2One or more of O.
Present invention also provides a kind of solid state battery, including the iron-based vulcanization prepared by preparation method described in such scheme
Thing electrode material.
This application provides a kind of preparation method of iron-based sulfide electrode material, it is comprised the following steps：By ferrous salt
Solution is added in polyvinyl alcohol water solution, and stirring obtains mixed solution.Under inert atmosphere protection, by above-mentioned mixed solution with
Sodium sulfide solution stirring mixing, obtains black precipitate after reaction.To be dried after black precipitate centrifuge washing, obtain last iron
Base sulfide electrode material.The application obtains iron-based sulfide electrode material using polyvinyl alcohol aid coprecipitation method, by Asia
During iron salt solutions mix with polyvinyl alcohol water solution, there is complex reaction in ferrous ion and polyvinyl alcohol, with vulcanization
During sodium water solution is co-precipitated, polyvinyl alcohol long-chain can not only be such that the coprecipitation reaction slowly carries out, moreover it is possible to effectively control
The pattern of precipitation.It is final to obtain the iron-based sulfide electrode material with the nanometer flower structure being made up of nanometer sheet.Two-dimensional sheet
The electrode material of structure is favorably improved contact of the electrode with solid electrolyte, shortens the transmission range of lithium ion and electronics.
Iron-based sulfide electrode material can improve the chemical property of solid state battery in the application, on the one hand be due to iron
Base sulfide has theoretical specific capacity and moderate operating voltage higher, is applied to that in solid state battery solid state battery can be improved
Energy density；Iron-based sulfide electrode material microscopic appearance is two-dimensional sheet structure in another aspect the application, by increasing capacitance it is possible to increase
The contact area of electrode and solid electrolyte, while alleviating the bulk effect in cyclic process, the circulation for improving solid state battery is steady
It is qualitative；Therefore, the iron-based sulfide electrode material that prepared by the application has preferable cycle performance.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of iron-based sulfide electrode material prepared by the embodiment of the present invention 1.
Fig. 2 is the cycle performance survey that iron-based sulfide electrode material prepared by the embodiment of the present invention 1 is applied to solid state battery
Attempt.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of composite polymer electrolyte, comprise the following steps：
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirring obtains mixed solution；In inert atmosphere protection
Under, above-mentioned mixed solution sodium sulfide solution is stirred and is mixed, black precipitate is obtained after reaction；
B) will be dried after black precipitate centrifuge washing, obtain last iron-based sulfide electrode material；
The application is prepared for iron-based sulfide electrode material using the method for polyvinyl alcohol aid coprecipitation, i.e. the present invention is adopted
The method prepared with co-precipitation obtains the iron-based sulfide with the nanometer flower structure and good cycling stability being made up of nanometer sheet
Electrode material.The preparation method of the iron-based sulfide electrode material that the application is provided, is self-assembled into iron-based sulfide nanometer sheet
Nano flower microstructure, helps to alleviate bulk effect, while increasing the contact area of electrode and solid electrolyte, improves solid-state
Battery overall performance.
In the present invention, the mixing of ferrous salt solution and polyvinyl alcohol water solution has been carried out first, and it is anti-that stirring occurs complexing
Should.Then above-mentioned mixed solution is mixed with sodium sulfide solution, stirring reaction for a period of time after, centrifuge washing is dried to obtain
Last product.
It is above-mentioned prepare mixed solution during, the ferrous salt for well known to those skilled in the art, to this this Shen
Please have no particular limits, example, herein described ferrous salt is preferably FeSO4·7H2O、FeCl2·4H2One kind in O
Or it is various, in embodiment, the polymeric matrix is more preferably FeSO4·7H2O.Herein described polyvinyl alcohol is preferably
The trade mark is 1,750 4 kinds of polyvinyl alcohol 2499, polyvinyl alcohol 1799, polyvinyl alcohol 1788 and polyvinyl alcohol.Herein described poly- second
Enol is that, used as complexing agent, it carries out ligand complex and forms Fe with ferrous ion2+- polyvinyl alcohol, then with S2-Mixing occurs altogether
Precipitation reaction iron-based sulfide electrode material of the generation with certain nanotopography.
The mixing temperature is preferably 0~100 DEG C, and the mixing time is 0.001~10h.Optimal is 1.0h.Institute
State and dry selection freeze-drying or 80 DEG C of vacuum drying, the drying time is preferably 12~36h.In embodiment more preferably
It is 18~32h, most preferably 24h.The whipping temp is too high, Fe2+Easily it is oxidized to Fe3+, produce impurity；
In iron-based sulfide electrode material prepared by the application, Fe2+There is complex reaction with polyvinyl alcohol chain, can be effective
Control reaction rate and product morphology, the iron-based sulfide electrode material of two-dimensional nano chip architecture can alleviate bulk effect, increase
Electrode and the contact area of solid electrolyte, shorten lithium ion transport distance.
Present invention also provides a kind of solid state battery, it includes the iron-based sulphur prepared by the preparation method described in such scheme
Compound electrode material.
The application prepare iron-based sulfide electrode material as solid state battery positive pole, due to iron-based sulfide electrode tool
There are preferable electron conduction and special nanostructured, and make lithium secondary battery that there is preferable high rate performance and stable circulation
Property.
For a further understanding of the present invention, the iron-based sulfide electrode material provided the present invention with reference to embodiment
Preparation method is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
FeSO4·7H2The O aqueous solution is added in the aqueous solution that concentration is 1.0wt%, the trade mark is polyvinyl alcohol 1750, room temperature
After stirring 0.5h, mixed solution is obtained；Then under argon gas atmosphere protection, it is 20wt%'s that mixed solution is added into concentration
Na2S·9H2In the O aqueous solution, room temperature reaction 0.5h, centrifuge washing black precipitate obtains iron-based sulfide electricity after freeze-drying 24h
Pole material.Microscopic appearance is as shown in Figure 1 for the iron-based sulfide electrode material of two-dimensional nano sheet.
With Li10GeP2S12-75Li2S·25P2S51%P2O5Two-layer solid-state electrolyte is made as conducting medium, lithium metal
It is, to electrode assembling into solid state battery, electrochemical property test to be carried out at ambient temperature.Curve is prepared for embodiment 1 in Fig. 2
Iron-based sulfide electrode material cycle performance, as shown in Figure 2, at room temperature, this application of electrode has in solid state battery
Preferable cycle performance, after circulating 30 times under 1000mA/g current densities, reversible capacity still keeps 436mAh/g or so.
Embodiment 2
FeSO4·7H2The O aqueous solution is added in the aqueous solution that concentration is 0.5wt%, the trade mark is polyvinyl alcohol 1799, room temperature
After stirring 0.5h, mixed solution is obtained；Then under argon gas atmosphere protection, it is 5wt%'s that mixed solution is added into concentration
Na2S·9H2In the O aqueous solution, room temperature reaction 0.5h, centrifuge washing black precipitate obtains iron-based sulphur after 24h is vacuum dried at 80 DEG C
Compound electrode material.Microscopic appearance is the iron-based sulfide electrode material of two-dimensional nano sheet.
With Li10GeP2S12-70Li2S·30P2S5, used as conducting medium, lithium metal is used as to electrode for two-layer solid-state electrolyte
Solid state battery is assembled into, electrochemical property test is carried out at ambient temperature.Iron-based sulfide electrode prepared by Application Example 2
Material assembles solid state battery, and after circulating 30 times under 800mA/g current densities, reversible capacity remains at 423mAh/g or so.
Embodiment 3
FeCl2·4H2The O aqueous solution is added in the aqueous solution that concentration is 3.0wt%, the trade mark is polyvinyl alcohol 1788, room temperature
After stirring 0.5h, mixed solution is obtained；Then under argon gas atmosphere protection, it is 20wt%'s that mixed solution is added into concentration
Na2S·9H2In the O aqueous solution, room temperature reaction 0.5h, centrifuge washing black precipitate obtains iron-based sulfide electrode after freeze-drying
Material.The nanometer flower structure that microscopic appearance is self-assembled into for nanometer sheet.
With Li10GeP2S12-80Li2S·20P2S5, used as conducting medium, lithium metal is used as to electrode for two-layer solid-state electrolyte
Solid state battery is assembled into, electrochemical property test is carried out at ambient temperature.Iron-based sulfide electrode prepared by Application Example 3
Material assembles solid state battery, and after circulating 30 times under 500mA/g current densities, reversible capacity remains at 352mAh/g or so.
Comparative example 1
Under argon gas atmosphere protection, FeSO4·7H2The O aqueous solution is added to the Na that concentration is 20wt%2S·9H2The O aqueous solution
In, room temperature reaction 0.5h, centrifuge washing black precipitate obtains iron-based sulfide electrode material, microscopic appearance after freeze-drying 24h
It is the second particle of nanoparticle agglomerates.
With Li10GeP2S12-75Li2S·25P2S51%P2O5Two-layer solid-state electrolyte is made as conducting medium, lithium metal
It is, to electrode assembling into solid state battery, electrochemical property test to be carried out at ambient temperature.Charge and discharge under 1000mA/g current densities
Electricity is followed, and reversible capacity only has 264mAh/g or so.This is primarily due to nanoparticle agglomerates causes active material and solid electrolytic
Matter contact area reduces, and interface resistance is raised.And larger volumetric expansion causes electrode to be destroyed in cyclic process, stable circulation
Property reduce.
Comparative example 2
Under argon gas atmosphere protection, FeSO4·7H2The O aqueous solution is added to the Na that concentration is 20wt%2S·9H2The O aqueous solution
In, room temperature reaction 0.5h, centrifuge washing black precipitate obtains iron-based sulfide electrode material after 24h is vacuum dried at 80 DEG C.It is micro-
Sight pattern is micron particles shape.
With Li10GeP2S12-70Li2S·30P2S5, used as conducting medium, lithium metal is used as to electrode for two-layer solid-state electrolyte
Solid state battery is assembled into, electrochemical property test is carried out at ambient temperature.At room temperature, this application of electrode is in solid state battery
In, under 800mA/g current densities after charge and discharge cycles 30 times, reversible capacity only has 282mAh/g.
Comparative example 3
FeCl3·6H2O(0.5mmol),Na2S·9H2O (2mmol) and S (2mmol) are dissolved in shape in 30mL deionized waters
Into the uniform aqueous solution.Then 10mL ethylenediamines are slowly added into the above-mentioned mixed solution being stirred continuously, and are subsequently transferred to water
In thermal response kettle, 160 DEG C of insulation 12h are heated to.It is super by deionized water and absolute ethyl alcohol after temperature naturally cools to room temperature
60 DEG C dry 5h acquisition presomas after sound cleaning.Presoma is placed in vacuum drying oven and is heated to 250 DEG C of insulation 2h acquisitions FeS.
Using organic electrolyte as conducting medium, lithium metal enters at ambient temperature as to electrode assembling into half-cell
Row electrochemical property test.Under 1000mA/g current densities after charge and discharge cycles 30 times, reversible capacity only has 257mAh/g.It is followed
Ring performance is significantly lower than solid state battery.And using organic electrolyte just in the potential safety hazard of leakage, burning and blast.
Comparative example 4
2g FeSO4·7H2O and 0.216g sucrose forms mixed solution in being dissolved in the deionized water of 7.5mL, 3.45g's
Na2S·9H2O is dissolved in 7.5mL deionized waters, and then above two solution is uniformly dispersed in the absolute ethyl alcohol of 15mL obtains
Suspension.Finally above-mentioned mixed solution is transferred in hydrothermal reaction kettle and is heated to 180 DEG C of insulation 18h.When temperature natural cooling
To room temperature, dried after deionized water and absolute ethanol washing and obtain final product FeS.
Using organic electrolyte as conducting medium, lithium metal enters at ambient temperature as to electrode assembling into half-cell
Row electrochemical property test, it is found that the decay of its reversible capacity is serious.At room temperature, this application of electrode is in solid state battery,
Reversible capacity only has 243mAh/g after charge and discharge cycles 30 times under 500mA/g current densities.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (9)
1. a kind of iron-based sulfide electrode material for being applied to solid state battery, it is characterised in that the iron based on conversion reaction
Base sulfide electrode material is selected from one or more of ferrous sulfide, ferriferrous sulfide and eight seven iron of vulcanization.
2. iron-based sulfide electrode material according to claim 1, it is characterised in that the FeS and Fe7S8Category four directions or
Hexagonal crystal system；The Fe3S4Category cubic system.
3. iron-based sulfide electrode material according to claim 1, it is characterised in that the FeS and Fe7S8Microcosmic sight
Pattern is the nanometer flower structure being made up of nanometer sheet, and any of which dimension is less than 100nm；The Fe3S4Microscopic appearance be by receiving
The nanometer flower structure of rice piece composition, any of which dimension is less than 100nm.
4. a kind of iron-based sulfide electrode material preparation method, it is characterised in that comprise the following steps：
A) ferrous salt solution is added in polyvinyl alcohol water solution, is stirred, obtain mixed solution；
B) under inert atmosphere protection, above-mentioned mixed solution is mixed with sodium sulfide solution stirring, is precipitated after reaction；
C dried after) pelleting centrifugation is washed, obtain iron-based sulfide electrode material.
5. preparation method according to claim 4, it is characterised in that the concentration of the ferrous salt solution be 1wt%~
80wt%；The concentration of the polyvinyl alcohol water solution is 0.01wt%~30wt%；The concentration of the sodium sulfide solution is
1wt%~80wt%.
6. preparation method according to claim 4, it is characterised in that the hybrid reaction temperature is 0~100 DEG C, time
It is 0.001~10h；
7. preparation method according to claim 4, it is characterised in that the drying is that freeze-drying or 80 DEG C of vacuum are done
Dry, drying time is 12~36h.
8. preparation method according to claim 4, it is characterised in that the ferrous salt is selected from FeSO4·7H2O and
FeCl2·4H2One or more of O.
9. a kind of solid state battery, it is characterised in that including the iron prepared by the preparation method described in any one of claim 4~7
Base sulfide electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611201709.3A CN106784815B (en) | 2016-12-23 | 2016-12-23 | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611201709.3A CN106784815B (en) | 2016-12-23 | 2016-12-23 | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106784815A true CN106784815A (en) | 2017-05-31 |
| CN106784815B CN106784815B (en) | 2019-09-10 |
Family
ID=58897521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611201709.3A Active CN106784815B (en) | 2016-12-23 | 2016-12-23 | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106784815B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461739A (en) * | 2018-03-23 | 2018-08-28 | 枣庄学院 | A kind of high performance lithium ionic cell cathode material Fe7S8The preparation method of/C |
| CN108682563A (en) * | 2018-04-17 | 2018-10-19 | 江苏大学 | A kind of Fe7S8@Fe5Ni4S8Combination electrode material and its preparation method and application |
| CN108687114A (en) * | 2018-05-16 | 2018-10-23 | 扬州杰嘉工业固废处置有限公司 | A kind of Organomercurial waste is stable and cures disposing technique |
| CN109004190A (en) * | 2018-07-11 | 2018-12-14 | 大同新成新材料股份有限公司 | A kind of ferrous sulfide anode material and preparation method |
| CN111517374A (en) * | 2020-04-20 | 2020-08-11 | 鸡西市唯大新材料科技有限公司 | Fe7S8Preparation method of/C composite material |
| CN111640952A (en) * | 2020-05-29 | 2020-09-08 | 天津大学 | Ferroferric sulfide electrode material and preparation method and application thereof |
| CN112661500A (en) * | 2021-01-07 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Biological ceramic bracket with micro-nano structure on surface and preparation method and application thereof |
| CN113140728A (en) * | 2021-04-26 | 2021-07-20 | 燕山大学 | Potassium iron sulfide thin film electrode and preparation method and application thereof |
| WO2022155254A1 (en) * | 2021-01-13 | 2022-07-21 | Form Energy, Inc. | Electrodes for alkaline iron batteries |
| US11611115B2 (en) | 2017-12-29 | 2023-03-21 | Form Energy, Inc. | Long life sealed alkaline secondary batteries |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735562A (en) * | 2003-01-17 | 2006-02-15 | 西巴特殊化学品控股有限公司 | A process for the production of porous inorganic materials or a matrix material containing nanoparticles |
| CN103415945A (en) * | 2011-02-28 | 2013-11-27 | 应用材料公司 | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
| CN105355871A (en) * | 2015-10-26 | 2016-02-24 | 中国科学院宁波材料技术与工程研究所 | Composite electrode material, preparation method thereof and all-solid-state lithium battery |
-
2016
- 2016-12-23 CN CN201611201709.3A patent/CN106784815B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1735562A (en) * | 2003-01-17 | 2006-02-15 | 西巴特殊化学品控股有限公司 | A process for the production of porous inorganic materials or a matrix material containing nanoparticles |
| CN103415945A (en) * | 2011-02-28 | 2013-11-27 | 应用材料公司 | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
| CN105355871A (en) * | 2015-10-26 | 2016-02-24 | 中国科学院宁波材料技术与工程研究所 | Composite electrode material, preparation method thereof and all-solid-state lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| JUN ZHENG等: ""Facile synthesis of magnetic Fe3S4 nanosheets and their application in lithium-ion storage"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11611115B2 (en) | 2017-12-29 | 2023-03-21 | Form Energy, Inc. | Long life sealed alkaline secondary batteries |
| CN108461739A (en) * | 2018-03-23 | 2018-08-28 | 枣庄学院 | A kind of high performance lithium ionic cell cathode material Fe7S8The preparation method of/C |
| CN108682563A (en) * | 2018-04-17 | 2018-10-19 | 江苏大学 | A kind of Fe7S8@Fe5Ni4S8Combination electrode material and its preparation method and application |
| CN108687114A (en) * | 2018-05-16 | 2018-10-23 | 扬州杰嘉工业固废处置有限公司 | A kind of Organomercurial waste is stable and cures disposing technique |
| CN108687114B (en) * | 2018-05-16 | 2021-05-11 | 扬州杰嘉工业固废处置有限公司 | Mercury-containing reagent waste stabilization and solidification treatment process |
| CN109004190A (en) * | 2018-07-11 | 2018-12-14 | 大同新成新材料股份有限公司 | A kind of ferrous sulfide anode material and preparation method |
| CN111517374B (en) * | 2020-04-20 | 2022-06-14 | 鸡西市唯大新材料科技有限公司 | Fe7S8Preparation method of/C composite material |
| CN111517374A (en) * | 2020-04-20 | 2020-08-11 | 鸡西市唯大新材料科技有限公司 | Fe7S8Preparation method of/C composite material |
| CN111640952A (en) * | 2020-05-29 | 2020-09-08 | 天津大学 | Ferroferric sulfide electrode material and preparation method and application thereof |
| CN112661500A (en) * | 2021-01-07 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Biological ceramic bracket with micro-nano structure on surface and preparation method and application thereof |
| WO2022155254A1 (en) * | 2021-01-13 | 2022-07-21 | Form Energy, Inc. | Electrodes for alkaline iron batteries |
| CN113140728B (en) * | 2021-04-26 | 2022-04-05 | 燕山大学 | Potassium iron sulfide thin film electrode and preparation method and application thereof |
| CN113140728A (en) * | 2021-04-26 | 2021-07-20 | 燕山大学 | Potassium iron sulfide thin film electrode and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106784815B (en) | 2019-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106784815B (en) | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery | |
| CN101662021B (en) | Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials | |
| Li et al. | Spinel LiNi0. 5Mn1. 5O4 as superior electrode materials for lithium-ion batteries: Ionic liquid assisted synthesis and the effect of CuO coating | |
| CN102130334B (en) | Graphene-based nano iron oxide composite material and preparation method thereof | |
| CN105591088B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN105355866B (en) | A kind of preparation method of cobaltosic oxide composite graphite alkene three-dimensional aeroge | |
| CN107611409A (en) | A kind of preparation method of flake nano FeS2/C negative materials | |
| US20140106223A1 (en) | METHODS FOR SURFACE COATING OF CATHODE MATERIAL LiNi0.5-XMn1.5MXO4 FOR LITHIUM-ION BATTERIES | |
| CN101662022B (en) | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials | |
| Liu et al. | Combustion synthesized macroporous structure MFe2O4 (M= Zn, Co) as anode materials with excellent electrochemical performance for lithium ion batteries | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN111710860B (en) | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof | |
| CN107293710A (en) | The preparation method of transition metal oxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN109192956B (en) | Lithium nickel cobalt aluminate anode material coated by lithium zirconium phosphate fast ion conductor and preparation method thereof | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN103872331A (en) | Aluminum cladding method for lithium ion positive electrode material | |
| CN107611374A (en) | A kind of preparation method of new lithium sulfur battery anode material | |
| CN104505500A (en) | Nanometer fusion lamination modified lithium ion battery positive electrode material and preparation method thereof | |
| CN104134782A (en) | Anode material for nanometer LiFePO4 lithium ion battery and preparation method thereof | |
| CN104638261A (en) | High rate LiFePO4/C positive electrode material and preparation method thereof | |
| CN111193022B (en) | Preparation and application of modified ammonium trifluorooxotitanate for lithium ion battery | |
| CN107381656B (en) | Preparation method of lithium ion battery negative electrode material | |
| CN105529460A (en) | Lithium-sulfur battery cathode material of lithium-sulfur battery, preparation method of cathode material and lithium-sulfur battery | |
| Islam et al. | A high voltage Li-ion full-cell battery with MnCo2O4/LiCoPO4 electrodes | |
| CN102185155B (en) | Nanometer ferric phosphate hollow sphere/graphene lithium ion battery 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 |