CN106784815B - 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
- CN106784815B CN106784815B CN201611201709.3A CN201611201709A CN106784815B CN 106784815 B CN106784815 B CN 106784815B CN 201611201709 A CN201611201709 A CN 201611201709A CN 106784815 B CN106784815 B CN 106784815B
- Authority
- CN
- China
- Prior art keywords
- iron
- electrode material
- preparation
- solution
- based sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 present invention provides a kind of iron-based sulfide electrode material, preparation method and the applications in solid state battery, belong to lithium secondary battery technical field.Iron-based sulfide electrode material based on conversion reaction is selected from the 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 the advantages that simple time saving.
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 technique
Lithium ion battery due to having many advantages, such as that energy density is high, discharge voltage is high, having extended cycle life and memory-less effect,
It is widely used in the fields 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 generallys use organic electrolyte as lithium ion conducting medium, exists
The safety issues such as inflammable, perishable and thermal stability 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 contacts electrolyte and can send out
Biochemical hair is answered, and generates one layer of non-uniform solid electrolyte film in metallic lithium surface.And due to electricity in charge and discharge process
Current density is unevenly distributed, and the solid electrolyte film that will lead to metallic lithium surface is cracked or even the case where fall off, lithium metal
Cathode constantly dissolves.In addition, the growth of Li dendrite will cause diaphragm puncture, eventually leads to battery short circuit and fail.
Solid state battery is replaced organic in conventional lithium ion battery using inorganic solid electrolyte or polymer dielectric
Electrolyte has higher security performance and thermal stability, it is considered to be thoroughly solves the problems, such as lithium ion battery security
Ultimate scheme.The inorganic solid electrolyte of most study includes sulfide solid electrolyte and solid oxide electrolyte two at present
Major class.Inorganic solid electrolyte material conductivity at room temperature with higher and mechanical strength, electrochemical window mouth width, thermostabilization
Property is good.And copolymer solid electrolyte is mainly using polyethylene oxide as the material system of matrix.The High temperature ion of this kind of material
Conductivity is higher, easily forms a film, and machining property is good.It is obvious using solid lithium battery security performance made of solid electrolyte
Better than liquid state batteries, the danger of leakage, burning and explosion that organic electrolyte occurs in use is efficiently solved.It is another
Aspect, the high mechanical strength of solid electrolyte can effectively inhibit the growth of Li dendrite, and not have interface side reaction, cyclical stability
It is significantly improved with security performance.Simultaneously but also lithium metal is applied to be possibly realized in battery as negative electrode material, into one
Step improves the energy density of battery.
Now widely used positive electrode is mostly lithium-containing transition metal oxide and phosphate electrode (LiCoO2,
LiMn2O4, LiNiO2, LiFePO4), this kind of material has high operating voltage and cyclical stability, but theoretical specific capacity is logical
Often lower, the ability for improving the energy density of battery is limited.Sulfenyl and transient metal sulfide electrode although operating voltage is lower,
But its theoretical specific capacity is very high, helps to improve the energy density of battery.In solid state battery, how to reduce interface resistance is to mention
High circulating battery stability, gives full play to the key point of positive electrode capacity.Existed using transient metal sulfide as positive electrode
Significant ground volume change is generally entailed in charge and discharge process, this may result in electrode dusting or electrode and electrolyte contacts boundary
There is the case where poor contact in face.Microscopic appearance is that the transient metal sulfide electrode material of sheet can be alleviated in cyclic process
Internal stress, inhibit volume change effect caused by electrode structure destruction.Meanwhile two-dimensional sheet structure has biggish ratio
Surface area can increase the contact area of electrode and solid electrolyte, reduce interface contact resistance, increase the work of electrochemical reaction
Property site.Thin nanometer sheet also contributes to shortening 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 environmental-friendly, specific capacity it is high have it is good
Research Prospects.Currently, generalling use the mistake of solvent heat and hydro-thermal method synthesis with certain microscopic appearance of complex process and time-consuming
Cross metal sulfide electrode material.Therefore, it develops simple timesaving synthetic method and obtains the iron-based sulfide with specific morphology
Electrode material is most important.
Summary of the invention
The present 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 the application due to iron-based sulfide theoretical specific capacity with higher and moderate operating voltage
It can be improved the energy density of solid state battery in solid state lithium battery；Iron-based sulfide electrode material is micro- in another aspect the application
Sight pattern is two-dimensional sheet structure, can increase the contact area of electrode and solid electrolyte, reduces interface contact resistance, simultaneously
Nanometer chip architecture can effectively shorten lithium ion transport distance, electrochemical reaction dynamics be improved, to improve solid state battery
Chemical property.Therefore, the iron-based sulfide electrode material of the application preparation has preferable cycle performance.
The present invention provides a kind of preparation method of iron-based sulfide electrode material, iron-based sulfide electricity provided by the present application again
The performance of solid state battery can be improved in pole material preparation method, specifically, by synthesis two-dimensional sheet active material, increase its with
The contact area of electrolyte and conductive additive alleviates the volume effect in cyclic process while reducing interface contact resistance
It answers, the final energy density and cyclical stability for improving solid state battery.
This application provides a kind of preparation methods of iron-based sulfide electrode material, comprising the following steps:
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirring to obtain mixed solution；In inert atmosphere protection
Under, above-mentioned mixed solution sodium sulfide solution is stirred, black precipitate is obtained after reaction.
B) will be dry after black precipitate centrifuge washing, obtain last iron-based sulfide electrode material.
Preferably, the aqueous solution for preparing raw material, the concentration of ferrous salt are 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 are 12~36h.
Preferably, the selected ferrous salt is FeSO4·7H2O and FeCl2·4H2O's is one or more.
Present invention also provides a kind of solid state batteries, including iron-based vulcanization prepared by preparation method described in above scheme
Object electrode material.
This application provides a kind of preparation methods of iron-based sulfide electrode material comprising following steps: by ferrous salt
Solution is added in polyvinyl alcohol water solution, stirring to obtain mixed solution.Under inert atmosphere protection, by above-mentioned mixed solution with
Sodium sulfide solution is stirred, and black precipitate is obtained after reaction.Will be dry 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, will be sub-
During iron salt solutions are mixed with polyvinyl alcohol water solution, complex reaction occurs for ferrous ion and polyvinyl alcohol, with vulcanization
During sodium water solution is co-precipitated, polyvinyl alcohol long-chain can not only be such that coprecipitation reaction slowly carries out, moreover it is possible to effectively control
The pattern of precipitating.It is final to obtain the iron-based sulfide electrode material with the nanometer flower structure being made of nanometer sheet.Two-dimensional sheet
The electrode material of structure helps to improve contact of the electrode with solid electrolyte, shortens the transmission range of lithium ion and electronics.
Iron-based sulfide electrode material can be improved the chemical property of solid state battery in the application, on the one hand be due to iron
Base sulfide theoretical specific capacity with higher and moderate operating voltage, applied to can be improved solid state battery in solid state battery
Energy density；Iron-based sulfide electrode material microscopic appearance is two-dimensional sheet structure in another aspect the application, can be increased
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 of the application preparation has preferable cycle performance.
Detailed description of the invention
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 below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation 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 methods of composite polymer electrolyte, comprising the following steps:
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirring to obtain mixed solution；In inert atmosphere protection
Under, above-mentioned mixed solution sodium sulfide solution is stirred, black precipitate is obtained after reaction；
B) will be dry 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 adopts
The iron-based sulfide having by the nanometer sheet nanometer flower structure formed and good cycling stability is obtained with the method for co-precipitation preparation
Electrode material.The preparation method of iron-based sulfide electrode material provided by the present application, 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 complexing occurs for stirring
It answers.Then above-mentioned mixed solution is mixed with sodium sulfide solution, after being stirred to react a period of time, centrifuge washing is dried to obtain
Last product.
It is above-mentioned prepare mixed solution during, the ferrous salt be it is well known to those skilled in the art, to this this Shen
It please be not particularly limited, exemplary, herein described ferrous salt is preferably FeSO4·7H2O、FeCl2·4H2One of O
Or it is a variety of, in embodiment, the polymeric matrix is more preferably FeSO4·7H2O.Herein described polyvinyl alcohol is preferably
The trade mark is polyvinyl alcohol 2499, polyvinyl alcohol 1799, polyvinyl alcohol 1788 and 1,750 4 kinds of polyvinyl alcohol.Herein described poly- second
Enol is to carry out ligand complex as complexing agent with ferrous ion and form Fe2+Polyvinyl alcohol, then with S2-Mixing occurs altogether
Precipitation reaction generates the iron-based sulfide electrode material 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
Dry selection freeze-drying or 80 DEG C of vacuum drying are stated, the drying time is preferably 12~36h.In embodiment more preferably
For 18~32h, most preferably for 24 hours.The whipping temp is excessively high, Fe2+Easily it is oxidized to Fe3+, generate impurity；
In the iron-based sulfide electrode material of the application preparation, Fe2+Complex reaction occurs with polyvinyl alcohol chain, it 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
The contact area of electrode and solid electrolyte shortens lithium ion transport distance.
Present invention also provides a kind of solid state batteries comprising iron-based sulphur prepared by preparation method described in above scheme
Compound electrode material.
Anode of the iron-based sulfide electrode material of the application preparation as solid state battery, since iron-based sulfide electrode has
There are preferable electron conduction and special nanostructure, and makes lithium secondary battery that there is preferable high rate performance and stable circulation
Property.
For a further understanding of the present invention, below with reference to embodiment to iron-based sulfide electrode material provided by the invention
Preparation method is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
FeSO4·7H2O 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 atmosphere protection, it is 20wt%'s that mixed solution, which is added to concentration,
Na2S·9H2In O aqueous solution, 0.5h, centrifuge washing black precipitate are reacted at room temperature, freeze-drying obtains iron-based sulfide electricity afterwards for 24 hours
Pole material.Microscopic appearance is that the iron-based sulfide electrode material of two-dimensional nano sheet is as shown in Figure 1.
With Li10GeP2S12-75Li2S·25P2S51%P2O5Two-layer solid-state electrolyte is made as conducting medium, lithium metal
, at solid state battery, to carry out electrochemical property test at room temperature to electrode assembling.Curve is the preparation of 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 recycling 30 times under 1000mA/g current density, reversible capacity still keeps 436mAh/g or so.
Embodiment 2
FeSO4·7H2O 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 atmosphere protection, it is 5wt%'s that mixed solution, which is added to concentration,
Na2S·9H2In O aqueous solution, 0.5h is reacted at room temperature, centrifuge washing black precipitate is dried in vacuo at 80 DEG C and obtains iron-based sulphur afterwards for 24 hours
Compound electrode material.Microscopic appearance is the iron-based sulfide electrode material of two-dimensional nano sheet.
With Li10GeP2S12-70Li2S·30P2S5Two-layer solid-state electrolyte is used as conducting medium, lithium metal to electrode
It is assembled into solid state battery, carries out electrochemical property test at room temperature.Iron-based sulfide electrode prepared by Application Example 2
Material assembles solid state battery, and after recycling 30 times under 800mA/g current density, reversible capacity remains at 423mAh/g or so.
Embodiment 3
FeCl2·4H2O 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 atmosphere protection, it is 20wt%'s that mixed solution, which is added to concentration,
Na2S·9H2In O aqueous solution, 0.5h is reacted at room temperature, centrifuge washing black precipitate obtains iron-based sulfide electrode after freeze-drying
Material.Microscopic appearance is the nanometer flower structure that nanometer sheet is self-assembled into.
With Li10GeP2S12-80Li2S·20P2S5Two-layer solid-state electrolyte is used as conducting medium, lithium metal to electrode
It is assembled into solid state battery, carries out electrochemical property test at room temperature.Iron-based sulfide electrode prepared by Application Example 3
Material assembles solid state battery, and after recycling 30 times under 500mA/g current density, reversible capacity remains at 352mAh/g or so.
Comparative example 1
Under argon atmosphere protection, FeSO4·7H2O aqueous solution is added to the Na that concentration is 20wt%2S·9H2O aqueous solution
In, 0.5h, centrifuge washing black precipitate are reacted at room temperature, freeze-drying obtains iron-based sulfide electrode material, microscopic appearance afterwards for 24 hours
For second particle made of nanoparticle agglomerates.
With Li10GeP2S12-75Li2S·25P2S51%P2O5Two-layer solid-state electrolyte is made as conducting medium, lithium metal
, at solid state battery, to carry out electrochemical property test at room temperature to electrode assembling.Charge and discharge under 1000mA/g current density
Electricity follows, and reversible capacity only has 264mAh/g or so.This, which is primarily due to nanoparticle agglomerates, leads to active material and solid electrolytic
Matter contact area reduces, and interface resistance increases.And biggish volume expansion causes electrode to be destroyed in cyclic process, stable circulation
Property reduce.
Comparative example 2
Under argon atmosphere protection, FeSO4·7H2O aqueous solution is added to the Na that concentration is 20wt%2S·9H2O aqueous solution
In, 0.5h is reacted at room temperature, centrifuge washing black precipitate is dried in vacuo at 80 DEG C and obtains iron-based sulfide electrode material afterwards for 24 hours.It is micro-
Sight pattern is micron particles shape.
With Li10GeP2S12-70Li2S·30P2S5Two-layer solid-state electrolyte is used as conducting medium, lithium metal to electrode
It is assembled into solid state battery, carries out electrochemical property test at room temperature.At room temperature, this application of electrode is in solid state battery
In, under 800mA/g current density 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 water
At uniform aqueous solution.Then 10mL ethylenediamine is slowly added into the above-mentioned mixed solution being stirred continuously, and is subsequently transferred to water
In thermal response kettle, it is heated to 160 DEG C of heat preservation 12h.It is super by deionized water and dehydrated alcohol after temperature cooled to room temperature
60 DEG C of dry 5h obtain presoma after sound cleaning.Presoma is placed in vacuum drying oven and is heated to 250 DEG C of heat preservation 2h acquisition FeS.
Using organic electrolyte as conducting medium, lithium metal be used as to electrode assembling at half-cell, at room temperature into
Row electrochemical property test.Under 1000mA/g current density 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 security risk of leakage, burning and explosion.
Comparative example 4
2g FeSO4·7H2O and 0.216g sucrose, which is dissolved in the deionized water of 7.5mL, forms mixed solution, 3.45g's
Na2S·9H2O is dissolved in 7.5mL deionized water, then is uniformly dispersed to obtain in the dehydrated alcohol of 15mL by above two solution
Suspension.Finally above-mentioned mixed solution is transferred in hydrothermal reaction kettle and is heated to 180 DEG C of heat preservation 18h.When temperature natural cooling
It is dry after deionized water and dehydrated alcohol washing to obtain final product FeS to room temperature.
Using organic electrolyte as conducting medium, lithium metal be used as to electrode assembling at half-cell, at room temperature into
Row electrochemical property test finds that the decaying 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 density.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to 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, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (6)
1. a kind of iron-based sulfide electrode material is in the application in solid state battery, which is characterized in that the iron-based sulfide electrode
Material is selected from FeS, Fe3S4And Fe7S8It is one or more；The FeS and Fe7S8Belong to four directions or hexagonal crystal system, the Fe3S4Belong to
Cubic system；Also, described FeS, Fe7S8、Fe3S4Microscopic appearance be the nanometer flower structure being made of nanometer sheet, wherein appointing
Dimension is lower than 100nm；
Also, the preparation method of the iron-based sulfide electrode material the following steps are included:
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirs, obtains mixed solution；
B) under inert atmosphere protection, above-mentioned mixed solution is stirred with sodium sulfide solution and is reacted, reaction temperature be 0~
100 DEG C, the time is 0.001~10h, is precipitated after reaction；
C) will be dry after precipitating centrifuge washing, obtain iron-based sulfide electrode material.
2. a kind of preparation method of iron-based sulfide electrode material, which comprises the following steps:
A) ferrous salt solution is added in polyvinyl alcohol water solution, stirs, obtains mixed solution；
B) under inert atmosphere protection, above-mentioned mixed solution is stirred with sodium sulfide solution and is reacted, reaction temperature be 0~
100 DEG C, the time is 0.001~10h, is precipitated after reaction；
C) will be dry after precipitating centrifuge washing, obtain iron-based sulfide electrode material.
3. preparation method according to claim 2, which is characterized 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%.
4. preparation method according to claim 2, which is characterized in that step C) described in drying be freeze-drying or
80 DEG C of vacuum drying, drying time are 12~36h.
5. preparation method according to claim 2, which is characterized in that the ferrous salt is selected from FeSO4·7H2O and
FeCl2·4H2O's is one or more.
6. a kind of solid state battery, which is characterized in that including iron prepared by preparation method described in any one of claim 2~5
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 CN106784815A (en) | 2017-05-31 |
| CN106784815B true 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) |
Families Citing this family (10)
| 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 |
| CN108682563B (en) * | 2018-04-17 | 2019-06-28 | 江苏大学 | A kind of Fe7S8@Fe5Ni4S8Combination electrode material and its preparation method and application |
| 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 |
| CN111640952B (en) * | 2020-05-29 | 2021-08-27 | 天津大学 | Ferroferric sulfide electrode material and preparation method and application thereof |
| CN112661500B (en) * | 2021-01-07 | 2022-06-14 | 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 |
| JP2024504099A (en) * | 2021-01-13 | 2024-01-30 | フォーム エナジー インク | 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 |
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 |
|---|
| "Facile synthesis of magnetic Fe3S4 nanosheets and their application in lithium-ion storage";Jun Zheng等;《Journal of Alloys and Compounds》;20160127;第668卷;第27-32页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106784815A (en) | 2017-05-31 |
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 | |
| CN107611409B (en) | Preparation method of flaky nano FeS2/C negative electrode material | |
| CN101662021B (en) | Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials | |
| CN105591088B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN107492655B (en) | molybdenum disulfide/carbon composite material and preparation method and application thereof | |
| CN108598410B (en) | Preparation method of lithium-sulfur battery interlayer material | |
| CN101662022B (en) | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials | |
| CN111710860B (en) | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN109879320B (en) | α-MoO3-xNano-belt and preparation method thereof, electrode material and energy storage device | |
| CN109192956B (en) | Lithium nickel cobalt aluminate anode material coated by lithium zirconium phosphate fast ion conductor and preparation method thereof | |
| CN108832114B (en) | Preparation method of graphene-coated CuFeO2 composite negative electrode material | |
| CN107611374A (en) | A kind of preparation method of new lithium sulfur battery anode material | |
| CN111193022B (en) | Preparation and application of modified ammonium trifluorooxotitanate for lithium ion battery | |
| CN107381656B (en) | Preparation method of lithium ion battery negative electrode material | |
| CN114464780A (en) | Nano-core-shell-inlaid nano-sheet-shaped ion battery negative electrode composite material and preparation method and application thereof | |
| CN111533186B (en) | Preparation method and application of spherical expanded molybdenum disulfide | |
| CN108878830A (en) | A kind of room temperature solid lithium-sulfur cell electrode material and preparation method thereof and solid-state lithium-sulfur cell | |
| CN107742710A (en) | A kind of preparation method of chromium base lithium ion battery composite cathode material | |
| CN106784724A (en) | A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons | |
| CN109616660A (en) | Cobaltosic oxide is carried on preparation method of carbon nanosheet electrode material and products thereof and application | |
| CN105789580B (en) | A kind of preparation method and applications of Copper-cladding Aluminum Bar zinc titanate lithium nano-particle | |
| CN115784189A (en) | Method for preparing lithium iron phosphate electrode material under hydrothermal magnetic field synergistic effect | |
| CN113517438B (en) | Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof | |
| CN112018379B (en) | Iron oxide composite graphene oxide nano material containing temperature-sensitive material and preparation method and application 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 |