CN106410195A - Preparation method of carbon-free lithium ferrous silicate lithium ion battery cathode material - Google Patents
Preparation method of carbon-free lithium ferrous silicate lithium ion battery cathode material Download PDFInfo
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- CN106410195A CN106410195A CN201611087986.6A CN201611087986A CN106410195A CN 106410195 A CN106410195 A CN 106410195A CN 201611087986 A CN201611087986 A CN 201611087986A CN 106410195 A CN106410195 A CN 106410195A
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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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- 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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- 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 preparation method of a carbon-free lithium ferrous silicate lithium ion battery cathode material. The preparation method comprises the following step that the Li2FeSiO4 cathode material is prepared by taking a silicon source, a lithium source and an iron source as raw materials through a hydrothermal reaction method, wherein the reaction temperature ranges from 150 DEG C to 400 DEG C, the pH ranges from 8 to 14, the reaction time ranges from 1 h to 10 h, an inorganic silicon-containing compound is adopted as the silicon source, an inorganic lithium-containing compound is adopted as the lithium source, and inorganic ferrous salt is adopted as the iron source. According to the preparation method, the nano-scale lithium ferrous silicate cathode material is prepared by taking the inorganic materials as raw materials in a reduction-free atmosphere, the obtained lithium ferrous silicate material does not contain carbon, the content of other impurities is very low, and the crystal morphology and the grain size of the material are easy to control. In addition, the preparation method is simple, easy to operate, short in reaction time, low in cost and suitable for industrialized mass production.
Description
Technical field
The present invention relates to a kind of preparation method of anode material of lithium battery, specifically one kind do not contain carbon lithium ion battery
The preparation method of silicate as positive pole material ferrous lithium.
Background technology
Silicates silicate as positive pole material ferrous lithium for lithium ion battery(Li2FeSiO4)There is stronger lattice steady
Determine effect, preferable cycle performance and high temperature safety, and two Li can be allowed on a molecular theory+Embedding de-, theoretical
Specific capacity is up to 332mAh/g it is considered to be one of lithium ion power battery cathode material of the next generation's most competitiveness.
At present, the method for synthetic silicic acid ferrous lithium mainly has three kinds, is solid sintering technology, sol-gal process and hydro-thermal respectively
Method, all employs Organic substance as pre-reaction material or additive in three of the above method.In Organic substance, the presence of carbon atom makes
Form reduction atmosphere, to guarantee the Li containing ferrous ion during obtaining reacting by heating2FeSiO4Formation, suppress anti-simultaneously
Fe during answering3O4Appearance.
But above-mentioned Li2FeSiO4Preparation process there are problems, be mainly manifested in following two aspects:First, pass
System synthetic method generated time is longer, and reaction needs to carry out under inert atmosphere or reducing atmosphere, complex process, and condition is severe
Carve;Second, Li in course of reaction2FeSiO4Crystal morphology develop and control sufficiently complex with crystallite dimension, and be readily incorporated in a large number
Impurity, is unfavorable for Li2FeSiO4The large-scale production of positive electrode.
Content of the invention
It is an object of the invention to provide a kind of preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium,
High to solve the problems, such as existing preparation method response time length, products obtained therefrom impurity content.
The present invention is realized in:A kind of preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium,
Comprise the following steps:With silicon source, lithium source and source of iron as raw material, Li is prepared using hydro-thermal reaction method2FeSiO4Positive electrode, reaction
Temperature is 150 ~ 400 DEG C,pH is 8 ~ 14, and the response time is 1 ~ 10h;Wherein, silicon source is silicon-containing inorganic compound, and lithium source is containing lithium
Inorganic compound, source of iron is inorganic divalent iron salt.
Preferably, the concretely comprising the following steps of the present invention:
(1)With silicon source and lithium source as raw material, before being prepared containing silicon and lithium using ball-milling method, sol-gal process or hydrothermal synthesis method
Drive thing, wherein, the consumption of silicon source and lithium source according to silicon atom and lithium atom mol ratio be 2 ~ 1: 1 ~ 3 ratio-dependent, and institute
State silicon source and lithium source is inorganic matters;
(2)The predecessor that gained is contained silicon and lithium is mixed with divalent iron salt and mixture is scattered in deionized water, then
AddpH regulator is adjustedpH-number is more than 8, obtains mixed liquor, and wherein, described divalent iron salt is inorganic molysite, and in described mixture, silicon is former
Son is 1: 1 with the mol ratio of iron atom, and lithium atom is not less than 2: 1 with the mol ratio of iron atom;If step(1)Middle preparation forerunner
When during thing, the mol ratio of lithium atom and silicon atom is less than 2: 1, need in step(2)The appropriate lithium source of middle addition, to ensure
In mixture, the ratio of lithium atom and iron atom is not less than 2: 1;
(3)Gained mixed liquor is reacted 1 ~ 10h in 150 ~ 400 DEG C in hydrothermal reaction kettle, reaction terminates rear filtering reacting liquid, institute
Obtain filter cake cleaned, dry, that is, obtain Li2FeSiO4Positive electrode.
Preferably, described silicon source is any one or a few in the oxide of silicon or the oxyacid of silicon, and described lithium source is
Any one or a few in the oxide of lithium, the oxysalt of the hydroxide of lithium, the halogenide of lithium or lithium.
It is highly preferred that described silicon source be silicon dioxide, orthosilicic acid, metasilicic acid, in two silicic acid or silica gel any one or
The mixture of two or more arbitrary proportions;Described lithium source is lithium nitrate, Lithium hydrate, lithium chloride, lithium sulfate, lithium iodide, bromination
The mixture of any one or two or more arbitrary proportion in lithium, lithium dihydrogen phosphate, lithium phosphate, lithium oxide or lithium nitrite.
Preferably, the consumption of described silicon source and lithium source according to silicon atom and lithium atom mol ratio be 1: 1 ~ 3 ratio true
Fixed, more preferably 1: 2 ~ 3.
Preferably, described divalent iron salt is ferrous phosphate, ferrous chloride, ferrous nitrate, ferrous sulfate, ferrous bromide, iodine
Change the mixture of any one or the two or more arbitrary proportion in ferrous, ferrous carbonate.
Preferably, describedpH regulator is sodium hydroxide, potassium hydroxide, Lithium hydrate, calcium hydroxide, magnesium hydroxide, oxygen
Change the mixture of sodium, potassium oxide, any one or two or more arbitrary proportion in magnesium oxide or calcium oxide.
Preferably, described reaction temperature is 200 ~ 350 DEG C, and the response time is 2 ~ 5h,pH is 11 ~ 14.
The present invention adopts inorganic material as raw material, and nanoscale ferrous metasilicate is obtained under the thermal and hydric environment no reducing atmosphere
Lithium anode material, no carbon in the middle of gained ferrous metasilicate lithium material, other impurities content is also very low, the crystal morphology of material
It is easily controlled with crystallite dimension, be conducive to regulating and controlling the intrinsic physical performance of ferrosilicon silicate of lithium.Due to prepared by the inventive method
Product in do not contain carbon, when using it for preparing lithium ion anelectrode, be that the control of conductive agent carbon content brings pole
Big convenience, is conducive to preparing the more excellent lithium ion anelectrode product of electric conductivity.The inventive method is in Li2FeSiO4
Preparation field be unprecedented, be the invention of novelty.
The inventive method is simple, reaction temperature is low, the response time is short, production efficiency is high, and raw material sources are extensively, all
For common, be easy to get, cheap industrialization commodity, low production cost, safety be good, suitable industrial mass production.
Brief description
Fig. 1 is the X-ray diffractogram of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope picture of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 1.
Fig. 4 is the PSD grain size analysis diagram of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 1.
Fig. 5 is the X-ray diffractogram of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 2.
Fig. 6 is the X-ray diffractogram of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 3.
Fig. 7 is the scanning electron microscope (SEM) photograph of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 3.
Fig. 8 is the PSD grain size analysis diagram of the ferrous metasilicate lithium material obtained by the embodiment of the present invention 3.
Fig. 9 is the X-ray diffractogram of the ferrous metasilicate lithium material obtained by comparative example 1.
Figure 10 is the scanning energy spectrum analysis figure of the ferrous metasilicate lithium material obtained by comparative example 1.
Specific embodiment
The invention provides a kind of preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium, it include with
Lower step:With silicon source, lithium source and source of iron as raw material, Li is prepared using hydro-thermal reaction method2FeSiO4Positive electrode, reaction temperature is
150 ~ 400 DEG C,pH is 8 ~ 14, and the response time is 1 ~ 10h;Wherein, silicon source is silicon-containing inorganic compound, and lithium source is inorganization containing lithium
Compound, source of iron is inorganic divalent iron salt;The consumption of silicon source and lithium source is 2 ~ 1: 1 ~ 3 according to the mol ratio of silicon atom and lithium atom
Ratio-dependent, the consumption of source of iron according to silicon atom and iron atom mol ratio be 1: 1 and the mol ratio of lithium atom and iron atom not
Ratio-dependent less than 2: 1.
The present invention is expanded on further with reference to specific embodiment, in following embodiment, do not describe in detail is various
Process and method are conventional methods as known in the art, and agents useful for same is that commercially available analysis is pure or chemical pure.
Embodiment 1
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 1: 2 ratio weigh phase respectively
The orthosilicic acid that should measure and lithium oxide, after both mix homogeneously, with ball-milling method ball milling 2h, rotating speed is 300r/min, prepared forerunner
Thing powder.
The preparation of mixed liquor:Gained predecessor powder and ferrous nitrate are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then mixture is scattered in deionized water, after mix homogeneously, adds sodium hydrate regulator solution
'spH-number is 14, obtains mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 3h at 250 DEG C, after reaction terminates, will be anti-
Liquid is answered to filter, gained filter cake cleans through deionized water, dries at 50 DEG C, that is, obtain khaki ferrous silicate lithium anode material
Material.
Gained ferrous metasilicate lithium material is shown as khaki under visible light, and contains carbon or Fe3O4Li2FeSiO4?
It is shown generically grey black under visible ray.The X ray diffracting spectrum of Fig. 1 shows, the main diffraction maximum of products obtained therefrom is orthogonal
Crystallographic system Li2FeSiO4Typical diffraction maximum, centre has no obvious Fe3O4Diffraction maximum;Fig. 2 is the scanning electron microscope (SEM) photograph of resulting materials,
The most Li of in figure display2FeSiO4Particle diameter is between 0.2-1 μm, also has individual particles to be grown to rhombic system crystal normal
The double Pedicellus et Pericarpium Trapae cone crystal forms seen;Show that crystal structure is in good condition by transmission electron microscope High Resolution Observations, as shown in Figure 3;The PSD of Fig. 4
Grain size analyses show that the average particle size of resulting materials is 3.15 μm, are likely due to partial particulate higher than scanning electron microscopic observation
Adhesion caused by.
Above analysis means of testing shows, the present invention is successfully prepared not carbon containing and Fe3O4Li2FeSiO4Material.
Embodiment 2
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 1: 2 ratio weigh phase respectively
The silicon dioxide that should measure and lithium oxide, will add deionized water after both mix homogeneously, and stir evenly, then mixed liquor is put into hydro-thermal
In reactor, 300 DEG C of reaction 2h, reaction is cleaned after terminating, filters, is dried, that is, obtain white powder precursors.
The preparation of mixed liquor:Gained predecessor powder and ferrous nitrate are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then mixture is dissolved in deionized water, after mix homogeneously, adds potassium hydroxide to adjust solutionpH-number is 14, obtains mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 2.5h at 200 DEG C, after reaction terminates, will
Reacting liquid filtering, gained filter cake is dried through at deionized water cleaning, 50 DEG C, that is, obtain ferrous silicate lithium anode material, its X-ray
Diffracting spectrum is as shown in Figure 5.
Embodiment 3
Weigh lithium oxide, silica gel and the nitric acid of respective amount according to the ratio that lithium atom, silicon atom and iron atom are 2: 1: 1 respectively
Ferrous iron, will add in deionized water after three's mix homogeneously, stirs evenly, add sodium hydrate regulator solutionpH-number is 14, obtains mixed
Close liquid.Then mixed liquor is put in hydrothermal reaction kettle, 300 DEG C of reaction 10h, cleaning after reaction terminates is filtered, is dried, that is, obtain
Coffee-like powder, as ferrous silicate lithium anode material.
The X ray diffracting spectrum of gained ferrous silicate lithium anode material is as shown in fig. 6, with respect to embodiment 1 and embodiment
2, embodiment 3 obtain ferrous metasilicate lithium material X-ray diffraction peak value generally low it means that using this scheme obtain silicon
Ferrous silicate lithium material average grain diameter is less than embodiment 1 and embodiment 2, does not observe obvious Fe in figure3O4Diffraction
Peak.It is respectively the scanning electron microscope (SEM) photograph of ferrous metasilicate lithium material and the grain size analysis diagram that embodiment 3 obtains, granularity shown in Fig. 7 and Fig. 8
The average-size of the crystal grain prepared by analysis display embodiment 3 is 1.48 μm.
Embodiment 4
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 1: 1 ratio weigh phase respectively
The metasilicic acid that should measure and lithium nitrate, after both mix homogeneously, with ball-milling method ball milling 2h, rotating speed is 300r/min, prepared forerunner
Thing powder.
The preparation of mixed liquor:Gained predecessor powder and ferrous chloride are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then adds lithium nitrate, the mol ratio of iron atom in lithium atom and aforementioned ferrous chloride in lithium nitrate
For 1: 1, then mixture is scattered in deionized water, after mix homogeneously, adds sodium hydrate regulator solutionpH-number is 13,
Obtain mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 2.5h at 250 DEG C, after reaction terminates, will
Reacting liquid filtering, gained filter cake is dried through at deionized water cleaning, 50 DEG C, that is, obtain ferrous silicate lithium anode material.
Embodiment 5
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 1: 2 ratio weigh phase respectively
The orthosilicic acid that should measure and lithium nitrate, after both mix homogeneously, with ball-milling method ball milling 2h, rotating speed is 300r/min, prepared forerunner
Thing powder.
The preparation of mixed liquor:Gained predecessor powder and ferrous sulfate are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then mixture is scattered in deionized water, after mix homogeneously, adds sodium hydrate regulator solution
'spH-number is 13, obtains mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 2h at 350 DEG C, after reaction terminates, will be anti-
Liquid is answered to filter, gained filter cake is dried through at deionized water cleaning, 50 DEG C, that is, obtain ferrous silicate lithium anode material.
Embodiment 6
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 1: 3 ratio weigh phase respectively
The silica gel that should measure and lithium chloride, after both mix homogeneously, with ball-milling method ball milling 2h, rotating speed is 300r/min, prepared predecessor
Powder.
The preparation of mixed liquor:Gained predecessor powder and ferrous carbonate are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then mixture is dissolved in deionized water, after mix homogeneously, adds sodium hydrate regulator solutionpH-number is 12, obtains mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 5h at 200 DEG C, after reaction terminates, will be anti-
Liquid is answered to filter, gained filter cake is dried through at deionized water cleaning, 50 DEG C, that is, obtain ferrous silicate lithium anode material.
Embodiment 7
Preparation containing silicon and the predecessor of lithium:According to silicon atom and lithium atom mol ratio be 2: 1 ratio weigh phase respectively
The orthosilicic acid that should measure and lithium oxide, after both mix homogeneously, with ball-milling method ball milling 2h, rotating speed is 300r/min, prepared forerunner
Thing powder.
The preparation of mixed liquor:Gained predecessor powder and ferrous nitrate are 1 according to the mol ratio of silicon atom and iron atom:
1 ratio mix homogeneously, then adds lithium oxide, and in lithium oxide, lithium atom and the mol ratio of aforementioned iron atom are 3: 2, then
Mixture is scattered in deionized water, after mix homogeneously, adds sodium hydrate regulator solutionpH-number is 11, obtains mixed liquor.
Hydro-thermal reaction:Above-mentioned mixed liquor is placed in hydrothermal reaction kettle, reacts 1h at 400 DEG C, after reaction terminates, will be anti-
Liquid is answered to filter, gained filter cake cleans through deionized water, dries at 50 DEG C, that is, obtain khaki ferrous silicate lithium anode material
Material.
Comparative example 1
Using tetraethyl orthosilicate, Ferrox. and Lithium hydrate as predecessor, by Li2FeSiO4Stoichiometric proportion weighs respectively
The predecessor of respective amount, hydro-thermal reaction 24h at 350 DEG C, after reaction terminates, by reacting liquid filtering, gained filter cake is through deionized water
Cleaning, dries at 50 DEG C, obtains product.
Products therefrom is in grey black, product is analyzed test, result is as shown in Fig. 9, Figure 10 and table 1.By X
Axial observation is visible, the Li that the product of the hydrothermal preparing process of carbon containing preparation is prepared with respect to the present invention2FeSiO4In thing phase composition
On there is no obvious advantage(That is it is fully achieved using the product that the carbon-free method of the present invention is obtained and be even more better than passing
The standard of product obtained by system carbon containing method), and by sem energy spectrum analysis figure(Figure 10)With scanning energy spectrum analysiss table(Table
1)As can be seen that containing substantial amounts of unformed shape carbon in the product being obtained using the hydro-thermal method of carbon containing, this gives Li2FeSiO4
Control as carbon content in the subsequent technique of positive electrode brings very big inconvenience.
Table 1 products therefrom element ratio
Claims (7)
1. a kind of preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium, is characterized in that, comprise the following steps:
With silicon source, lithium source and source of iron as raw material, Li is prepared using hydro-thermal reaction method2FeSiO4Positive electrode, reaction temperature is 150 ~ 400
DEG C,pH is 8 ~ 14, and the response time is 1 ~ 10h;Wherein, described silicon source is inorganic silicon-containing compound, and described lithium source is inorganic containing lithium
Compound, described source of iron is inorganic divalent iron salt.
2. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 1, its feature
It is to comprise the following steps:First the predecessor containing silicon and lithium, the use of described silicon source and lithium source are prepared for raw material with silicon source and lithium source
Measure the ratio-dependent that the mol ratio according to silicon atom and lithium atom is 2 ~ 1: 1 ~ 3;
The predecessor again gained being contained silicon and lithium is mixed with source of iron and mixture is scattered in deionized water, is subsequently addingpH
Regulator is adjustedpH-number is more than 8, obtains mixed liquor, and in described mixture, the mol ratio of silicon atom and iron atom is 1: 1, and lithium atom with
The mol ratio of iron atom is not less than 2: 1;
Then gained mixed liquor is placed in hydrothermal reaction kettle and is reacted, question response terminates rear filtering reacting liquid, gained filter cake
Cleaned, dry, that is, obtain Li2FeSiO4Positive electrode.
3. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 1 and 2, it is special
Levying is, described silicon source is any one or a few in the oxide of silicon or the oxyacid of silicon, described lithium source be lithium oxide,
Any one or a few in the oxysalt of the hydroxide of lithium, the halogenide of lithium or lithium.
4. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 3, its feature
It is that described silicon source is any one or two or more any ratio in silicon dioxide, orthosilicic acid, metasilicic acid, two silicic acid or silica gel
The mixture of example;Described lithium source be lithium nitrate, Lithium hydrate, lithium chloride, lithium sulfate, lithium iodide, lithium bromide, lithium dihydrogen phosphate,
The mixture of any one or two or more arbitrary proportion in lithium phosphate, lithium oxide or lithium nitrite.
5. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 2, its feature
Be, the consumption of described silicon source and lithium source according to silicon atom and lithium atom mol ratio be 1: 1 ~ 3 ratio-dependent.
6. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 1 and 2, it is special
Levying is, described source of iron is ferrous phosphate, ferrous chloride, ferrous nitrate, ferrous sulfate, ferrous bromide, iron iodide, ferrous carbonate
In any one or two or more arbitrary proportion mixture.
7. the preparation method without carbon lithium ion cell positive material ferrosilicon silicate of lithium according to claim 2, its feature
It is, describedpH regulator be sodium hydroxide, potassium hydroxide, Lithium hydrate, calcium hydroxide, magnesium hydroxide, sodium oxide, potassium oxide,
The mixture of any one or two or more arbitrary proportion in magnesium oxide or calcium oxide.
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CN108735995A (en) * | 2018-05-24 | 2018-11-02 | 桑德集团有限公司 | Composite material and preparation method, cell positive material and battery |
CN110364729A (en) * | 2019-07-01 | 2019-10-22 | 湖北锂诺新能源科技有限公司 | Witch culture ferrous silicate lithium anode material and preparation method thereof |
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CN102219230A (en) * | 2011-05-17 | 2011-10-19 | 中南大学 | Method for preparing ferrous silicate lithium of anode material of lithium ion battery |
CN103400981A (en) * | 2013-07-03 | 2013-11-20 | 国家纳米科学中心 | Hexagonal walnut iron lithium silicate aggregation and preparation method thereof |
CN103915627A (en) * | 2014-04-19 | 2014-07-09 | 河南工业大学 | Method for preparing Li2FeSiO4 positive material by hot isostatic pressing method |
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CN102219230A (en) * | 2011-05-17 | 2011-10-19 | 中南大学 | Method for preparing ferrous silicate lithium of anode material of lithium ion battery |
CN103400981A (en) * | 2013-07-03 | 2013-11-20 | 国家纳米科学中心 | Hexagonal walnut iron lithium silicate aggregation and preparation method thereof |
CN103915627A (en) * | 2014-04-19 | 2014-07-09 | 河南工业大学 | Method for preparing Li2FeSiO4 positive material by hot isostatic pressing method |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108735995A (en) * | 2018-05-24 | 2018-11-02 | 桑德集团有限公司 | Composite material and preparation method, cell positive material and battery |
CN110364729A (en) * | 2019-07-01 | 2019-10-22 | 湖北锂诺新能源科技有限公司 | Witch culture ferrous silicate lithium anode material and preparation method thereof |
CN110364729B (en) * | 2019-07-01 | 2022-10-18 | 湖北锂诺新能源科技有限公司 | Tungsten-doped ferrous silicate lithium cathode material and preparation method thereof |
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