CN103887493A - Anode material for lithium ion battery and preparation method of anode material - Google Patents
Anode material for lithium ion battery and preparation method of anode material Download PDFInfo
- Publication number
- CN103887493A CN103887493A CN201410062014.6A CN201410062014A CN103887493A CN 103887493 A CN103887493 A CN 103887493A CN 201410062014 A CN201410062014 A CN 201410062014A CN 103887493 A CN103887493 A CN 103887493A
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- Prior art keywords
- lithium
- anode material
- lithium ion
- fluoro
- ferric sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- 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
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an anode material for a lithium ion battery and a preparation method of the anode material. The anode material is fluoro lithium ferric sulfate which is obtained by performing solid-phase reaction on a precursor FeSO4.7H2O and LiF after being ball-milled and mixed. The preparation method of the anode material particularly comprises the following steps: putting the precursor and absolute ethyl alcohol in a zirconium oxide ball-milling tank for high energy ball milling to obtain a mixture; after milling for 24 hours, putting the mixture in a vacuum drying box to be dried for 24 hours at 60 DEG C; after alcohol is fully volatilized, manually grinding the mixture to fine powder in an agate mortar; then compacting to a round tablet; and putting in a ceramic boat and performing solid phase sintering under protection of a reducing atmosphere or inertial gas at 350-380 DEG C to prepare the fluoro lithium ferric sulfate anode material. The anode material has the characteristics of high capacity, good stability and high open-circuit voltage. The fluoro lithium ferric sulfate prepared by adopting the method is taken as an active material of the anode to prepare the lithium ion battery. The lithium ion battery has the relatively great first-time specific discharge capacity and the good rate capability.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery, due to advantages such as its energy is high, environmental protection, life-span length, has been subject to people's extensive concern, and positive electrode is most important on the impact of lithium ion battery overall performance! Common positive electrode has cobalt acid lithium LiCoO
2, LiMn2O4 LiMn
2o
4, LiFePO4 LiFePO
4, and the doping of these materials, coated or low-dimensional form.LiFePO
4due to cheap, stable performance and environment-protecting asepsis, once be considered to the especially desirable positive electrode of electrokinetic cell of the most promising lithium ion battery, but itself there is low electron conduction and ionic conductivity, this just requires it to carry out, and carbon is coated or particle nanometer is further improved, and Tarascon J-M seminar adopts [SO by introducing fluorine atom recently
4f]
3-replace [PO
4]
3-successfully prepare novel fluoro polyanion type positive electrode LiFeSO
4f, demonstrates higher than LiFePO
4voltage platform, better lithium ion transmission dynamic performance and high ionic conductivity, make this material also can reach high high rate performance without nanometer, but LiFeSO
4f is unstable in water, easily decomposes, and can not prepare by low-temperature aqueous solution process, and conventional preparation method is that this just easily causes environmental pollution and improved preparation cost by introducing the hot method of ion of ionic liquid as reaction media.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose a kind of anode material for lithium-ion batteries and preparation method thereof.
A kind of anode material for lithium-ion batteries in the present invention is precursor FeSO
47H
2there is the fluoro ferric sulfate lithium material of solid phase reaction gained in O and LiF, the powder particle particle diameter of this material is 50 nm ~ 300 nm after ball milling mixes.
Described precursor material FeSO
47H
2mole proportioning of O and LiF is between 1:1 ~ 1:2.
Described precursor material FeSO
47H
2o and LiF purity range are 99% ~ 99.999%, and mechanical milling process is high-energy ball milling, and it is to carry out in vacuum furnace that solid phase reaction process occurs.
The method of preparing above-mentioned anode material for lithium-ion batteries is: precursor and absolute ethyl alcohol are put into zirconia ball grinding jar and carry out high-energy ball milling; after 24h ball milling; mixture is put into 60 ℃ of dry 24 h of vacuum drying chamber; treat that alcohol volatilizees completely; mixture hand lapping in agate mortar is become to fine-powdered; then be compacted into disk, put into 350 ℃ ~ 380 ℃ of ceramic boat solid-phase sintering under reducing atmosphere or inert atmosphere protection and make fluoro ferric sulfate lithium anode material.
The temperature that solid phase reaction wherein occurs is controlled between 350 ℃ ~ 380 ℃, and the reaction time is 2 h ~ 3 h.Before solid phase reaction, vacuum furnace is evacuated to below 0.5 Pa, course of reaction need pass into protective gas always and close below gas until experiment end temp is down to 80 ℃.
It is the mist of reducibility gas or inert gas or reproducibility and inert gas that the protective gas that the sintering process of solid phase reaction passes into wherein occurs; described reducibility gas comprises one or both of hydrogen, carbon monoxide; described inert gas comprises one or both in nitrogen, argon gas, and in described mist, the dividing potential drop of reducibility gas is more than 50%.
According to the constructed lithium ion battery of above-mentioned positive electrode, its electrolyte is nonaqueous electrolyte, negative pole forms by having the negative electrode active material that can embed and deviate from lithium ion, anodal form by having the positive active material that can embed and deviate from lithium ion, having the positive active material that can embed and deviate from lithium ion is exactly above-mentioned fluoro ferric sulfate lithium anode material.
The preparation method of the anode material for lithium-ion batteries that the present invention proposes, be a kind of simple, fast, the non-hydrated of preparing anode material for lithium-ion batteries fluoro ferric sulfate lithium of environmental protection becomes method, and the hot method of conventional ion has increased preparation cost and introduce ionic liquid etc. and easily cause environmental pollution.According to the prepared lithium ion battery of positive electrode of the present invention, demonstrate higher first discharge specific capacity and good high rate performance.
Accompanying drawing explanation
The X-ray diffractogram of the prepared fluoro ferric sulfate lithium anode material of Fig. 1.
The SEM figure of the prepared fluoro ferric sulfate lithium anode material of Fig. 2.
The x-ray photoelectron energy spectrogram of the prepared fluoro ferric sulfate lithium anode material of Fig. 3.
Fig. 4 adopts the cyclic voltammogram of prepared fluoro ferric sulfate lithium as the battery of anode material for lithium-ion batteries.
Fig. 5 adopts the constant current charge-discharge figure of prepared fluoro ferric sulfate lithium as the battery of anode material for lithium-ion batteries.
Embodiment
Further describe the present invention below by specific embodiment:
Embodiment 1, by precursor FeSO
47H
2o (99.9%) and LiF (99.9%) put into zirconia ball grinding jar by 1:1.2 mol ratio together with absolute ethyl alcohol (consumption is for flooding ball milling pearl and abrasive material) and carry out high-energy ball milling; after 24 h ball millings; mixture is put into 60 ℃ of dry 24 h of vacuum drying chamber; treat that alcohol volatilizees completely; mixture hand lapping in agate mortar is become to fine-powdered; then be compacted into disk, put into 380 ℃ of ceramic boat solid-phase sintering 2 h under the protection of inert nitrogen gas and make fluoro ferric sulfate lithium (LiFeSO
4f) positive electrode, if Fig. 1 is the X-ray diffractogram of positive electrode of preparation, Fig. 2 is the SEM figure of prepared positive electrode.
Embodiment 2, by precursor FeSO
47H
2o (99.9%) and LiF (99.9%) put into zirconia ball grinding jar by 1:1 mol ratio together with absolute ethyl alcohol (consumption is for flooding ball milling pearl and abrasive material) and carry out high-energy ball milling; after 24 h ball millings; mixture is put into 60 ℃ of dry 24 h of vacuum drying chamber; treat that alcohol volatilizees completely; mixture hand lapping in agate mortar is become to fine-powdered; then be compacted into disk, put into 380 ℃ of ceramic boat solid-phase sintering 2 h under the protection of inert gas argon gas and make fluoro ferric sulfate lithium (LiFeSO
4f) positive electrode, if Fig. 3 is the x-ray photoelectron energy spectrogram of prepared fluoro ferric sulfate lithium.
Embodiment 3, by precursor FeSO
47H
2o (99.9%) and LiF (99.9%) put into zirconia ball grinding jar by 1:1.2 mol ratio together with absolute ethyl alcohol (consumption is good for flooding ball milling pearl and abrasive material) and carry out high-energy ball milling; after 24 h ball millings; mixture is put into 60 ℃ of dry 24h of vacuum drying chamber; treat that alcohol volatilizees completely; mixture hand lapping in agate mortar is become to fine-powdered; then be compacted into disk, put into 380 ℃ of ceramic boat solid-phase sintering 2 h under the protection of inert nitrogen gas and make fluoro ferric sulfate lithium (LiFeSO
4f) positive electrode; By the LiFeSO making
4f positive active material is ground to particle diameter and is less than below 7 μ m, sieves, and takes active material, acetylene black, binding agent PVDF by the proportioning of quality 8:1:1, add NMP, 80 ℃ of constant temperature stir 4 h, are mixed with electrode slurry, film be cut into 0.8 × 0.8 cm on clean aluminium foil
2electrode slice, with LiPF
6for electrolyte, lithium sheet is that negative pole is assembled into lithium ion battery and tests, between 2.0 ~ 4.5V, carry out cyclic voltammetric and constant current charge-discharge, result shows, battery has obvious redox reversible process, and have higher first discharge specific capacity, first discharge specific capacity is 115 mAh/g, after 20 2C discharge and recharge, Capacitance reserve is in 70 mAh/g left and right.As Figure 4 and 5 are respectively the electrograph that charges and discharge under the cyclic voltammetric of the battery that adopts the assembling of prepared positive electrode and different multiplying.
Claims (8)
1. an anode material for lithium-ion batteries, is characterized in that: this positive electrode is precursor FeSO
47H
2there is the fluoro ferric sulfate lithium material of solid phase reaction gained in O and LiF, the powder particle particle diameter of this material is 50 nm ~ 300 nm after ball milling mixes.
2. a kind of anode material for lithium-ion batteries according to claim 1, is characterized in that: precursor material FeSO
47H
2mole proportioning of O and LiF is between 1:1 ~ 1:2.
3. a kind of anode material for lithium-ion batteries according to claim 1, is characterized in that: precursor material FeSO
47H
2o and LiF purity range are 99% ~ 99.999%, and mechanical milling process is high-energy ball milling, and it is to carry out in vacuum furnace that solid phase reaction process occurs.
4. prepare the method for anode material for lithium-ion batteries as claimed in claim 1 for one kind; it is characterized in that: precursor and absolute ethyl alcohol are put into zirconia ball grinding jar and carry out high-energy ball milling; after 24h ball milling; mixture is put into 60 ℃ of dry 24 h of vacuum drying chamber; treat that alcohol volatilizees completely; mixture hand lapping in agate mortar is become to fine-powdered; then be compacted into disk, put into 350 ℃ ~ 380 ℃ of ceramic boat solid-phase sintering under reducing atmosphere or inert atmosphere protection and make fluoro ferric sulfate lithium anode material.
5. the preparation method of anode material for lithium-ion batteries according to claim 4, is characterized in that: the temperature that solid phase reaction occurs is controlled between 350 ℃ ~ 380 ℃, and the reaction time is 2 h ~ 3 h; Before solid phase reaction, vacuum furnace is evacuated to below 0.5 Pa, course of reaction need pass into protective gas always and close below gas until experiment end temp is down to 80 ℃.
6. the preparation method of anode material for lithium-ion batteries according to claim 5; it is characterized in that: the protective gas that the sintering process of generation solid phase reaction passes into is the mist of reducibility gas or inert gas or reproducibility and inert gas; described reducibility gas comprises one or both of hydrogen, carbon monoxide; described inert gas comprises one or both in nitrogen, argon gas, and in described mist, the dividing potential drop of reducibility gas is more than 50%.
7. a lithium ion battery, its electrolyte is nonaqueous electrolyte, negative pole forms by having the negative electrode active material that can embed and deviate from lithium ion, anodal form by thering is the positive active material that can embed and deviate from lithium ion, it is characterized in that: having the positive active material that can embed and deviate from lithium ion is fluoro ferric sulfate lithium anode material as claimed in claim 1.
8. a kind of lithium ion battery according to claim 7, is characterized in that: the positive electrode fluoro ferric sulfate lithium active material of lithium ion battery is less than below 7 μ m through being ground to particle diameter.
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| CN201410062014.6A CN103887493A (en) | 2014-02-24 | 2014-02-24 | Anode material for lithium ion battery and preparation method of anode material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980202A (en) * | 2019-03-26 | 2019-07-05 | 湖北锂诺新能源科技有限公司 | The preparation method of titanium doped and titanium phosphate sodium cladding fluorosulfuric acid ferrous iron lithium anode material |
| CN112349965A (en) * | 2020-10-14 | 2021-02-09 | 双登集团股份有限公司 | Lithium iron phosphate lithium ion battery with improved low-temperature performance and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282097A (en) * | 2008-10-23 | 2011-12-14 | 国立科学研究中心 | Fluorosulphates useful as electrode materials |
| CN102332580A (en) * | 2011-03-15 | 2012-01-25 | 中国科学院物理研究所 | Fluorinated ferric sulfate salt compound as well as preparation method and application thereof |
| CN102361071A (en) * | 2011-06-27 | 2012-02-22 | 湖南中天新能源有限公司 | Preparation method for modified LiFePO4 lithium ion battery anode material |
-
2014
- 2014-02-24 CN CN201410062014.6A patent/CN103887493A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282097A (en) * | 2008-10-23 | 2011-12-14 | 国立科学研究中心 | Fluorosulphates useful as electrode materials |
| CN102332580A (en) * | 2011-03-15 | 2012-01-25 | 中国科学院物理研究所 | Fluorinated ferric sulfate salt compound as well as preparation method and application thereof |
| CN102361071A (en) * | 2011-06-27 | 2012-02-22 | 湖南中天新能源有限公司 | Preparation method for modified LiFePO4 lithium ion battery anode material |
Non-Patent Citations (2)
| Title |
|---|
| JINPING DONG等: ""Triplite LiFeSO4F as cathode material for Li-ion batteries"", 《JOURNAL OF POWER SOURCES》, vol. 244, 1 December 2012 (2012-12-01), pages 716 - 720, XP028691988, DOI: doi:10.1016/j.jpowsour.2012.11.084 * |
| M. ATI等: ""Synthesis and electrochemical properties of pure LiFeSO4F in the triplite structure"", 《ELECTROCHEMISTRY COMMUNICATIONS》, vol. 13, no. 11, 22 August 2011 (2011-08-22), pages 1280 - 1283 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109980202A (en) * | 2019-03-26 | 2019-07-05 | 湖北锂诺新能源科技有限公司 | The preparation method of titanium doped and titanium phosphate sodium cladding fluorosulfuric acid ferrous iron lithium anode material |
| CN112349965A (en) * | 2020-10-14 | 2021-02-09 | 双登集团股份有限公司 | Lithium iron phosphate lithium ion battery with improved low-temperature performance and preparation method thereof |
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