CN109295312A - A kind of method of remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor - Google Patents
A kind of method of remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor Download PDFInfo
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- CN109295312A CN109295312A CN201811067306.3A CN201811067306A CN109295312A CN 109295312 A CN109295312 A CN 109295312A CN 201811067306 A CN201811067306 A CN 201811067306A CN 109295312 A CN109295312 A CN 109295312A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods of lithium remaining in circulation and stress hydro-thermal legal system electrode material reaction mother liquor, lithium hydroxide is added to reaction mother liquor, solid-liquid is separated after heating reaction, separates solid-liquid again after sediment and phosphatase reaction, obtains the raw material that clear solution is used as hydro-thermal legal system electrode material；The clear solution separated for the first time is passed through into ion exchange UF membrane lithium sulfate, remaining solvent concentration recycles, obtained lithium sulfate aqueous solution passes through Bipolar Membrane, lithium ion is separated with sulfate ion, and lithium hydroxide solution and sulfuric acid solution are finally respectively obtained in conjunction with the hydroxide ion and hydrogen ion that water electrolysis obtains respectively；It is used as the raw material of hydro-thermal legal system electrode material after lithium hydroxide solution is concentrated.Method of the invention is applied widely, significantly reduces the cost of material of hydro-thermal method technique production, does not add new raw material, circulation and stress effect is good, and process is simple, cost performance is high, is conducive to promote and apply in industrialized production.
Description
Technical field
The invention belongs to electrode material of lithium battery fields, and in particular to a kind of circulation and stress hydro-thermal legal system electrode material reaction
The method of remaining lithium in mother liquor.
Background technique
With the phosphate metal lithium salt compound of olivine structural in lithium ion battery, such as LiFePO4, cobalt phosphate lithium, phosphorus
Sour nickel lithium, iron manganese phosphate for lithium, lithium manganese phosphate etc., can be used as lithium ion secondary battery anode material, and wherein LiFePO4 has been
It is widely used in the fields such as integral new-energy passenger, light wind-powered electricity generation energy storage.
The Industrialized processing technique of existing olivine structural electrode material is using high temperature solid-state method as mainstream, but high temperature solid-state method
A large amount of pollution gas, and its batch consistency of electrode material and stay in grade of this method preparation can be generated in sintering process
Property is bad, and low temperature and high rate performance are poor.
Since hydro-thermal method is to prepare olivine structural electrode material by the mixing of molecular level, reaction in dicyandiamide solution
Material, be capable of the batch consistency and quality stability of accurately coordination electrode material, and electrode material obtained in this way
Material low temperature and high rate performance are excellent in.Olive all is prepared in research hydro-thermal method compared with multiple enterprises and mechanism currently, having both at home and abroad
The industrialization technology of stone structure electrode material, such as BYD, South Korea Han Hua, Hebei University of Technology, Canada Phostech.
Hydro-thermal method produces the phosphate metal lithium salts of olivine structural, with H3PO4+3LiOH+FeSO4=LiFePO4↓+Li2SO4
+3H2For O, reaction mother liquor is after raw material mixes in dicyandiamide solution, reacts obtained olivine structural electrode material, will to consolidate
Remaining filtrate after phase electrode material filtering, including the object that dissolves each other of water or organic solvent or water and organic solvent, instead
Should not exclusively or raw material institute with impurity it is existing on a small quantity other metal cation (one kind of Fe ion, Mn ion, Co ion etc.
Or it is a variety of) and anion (phosphate anion) and remnants a large amount of lithium.Remaining lithium causes hydro-thermal method technique to prepare electrode material
Production (raw material) higher cost of material, this is but also hydro-thermal method technique is difficult to the industrialization in electrode material of lithium battery at this stage
It is applied on a large scale in production.
There are some researchs to start to explore the method for sufficiently recycling lithium in hydro-thermal method mother liquor, patent now
CN107915239A discloses a kind of method for preparing high-purity sulfuric acid lithium with LiFePO4 reaction mother liquor, and this method can obtain pure
Degree 99% or more lithium sulfate, but the method can only be directed to LiFePO 4 material reaction mother liquor, narrow application range, and
The lithium sulfate for introducing sodium ion, and being recovered to cannot be utilized directly as the feedstock circulation of hydro-thermal reaction, be reduced using valence
Value.In addition, there are also some chemical methodes, precipitating reagent such as barium hydroxide is added into reaction mother liquor, is obtained after separating barium sulfate precipitate
To lithium hydroxide, but this method can introduce new impurity (such as barium ions), and lose part organic solvent, and additionally extend system
Standby process increases preparation control difficulty and energy consumption, and recovery scheme sexual valence is relatively low, easily causes adverse effect to environment.
For this purpose, the present invention is by providing a kind of recycling hydro-thermal method, to prepare the reaction of olivine structural electrode material female
Remaining lithium in liquid is greatly reduced hydro-thermal method technique production (raw material) cost, enables hydro-thermal method technique in industrialized production
Middle realization is large-scale to be promoted and applied.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of circulation and stress hydro-thermal legal system electrode materials
Expect the method for remaining lithium in reaction mother liquor.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of method of remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor, comprising:
1) lithium hydroxide is added into hydro-thermal legal system electrode material reaction mother liquor sufficiently to react, then separates solid-liquid and obtains the
One clear solution and the first sediment；
2) the first sediment is mixed with phosphoric acid solution, sufficiently after reaction, separation solid-liquid obtains the second clear solution and the
Second clear solution is used as the raw material of hydro-thermal legal system electrode material by two sediments；
3) by the first clear solution by amberplex, separation lithium sulfate obtains lithium sulfate aqueous solution；
4) separate lithium ion with sulfate ion by Bipolar Membrane isolated lithium sulfate aqueous solution, and respectively
In conjunction with the hydroxide ion and hydrogen ion that water electrolysis obtains, lithium hydroxide solution and sulfuric acid solution, lithium hydroxide are respectively obtained
It is used as the raw material of hydro-thermal legal system electrode material after solution is concentrated.
Further, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 1) uses
Then reaction mother liquor is heated to 60-100 DEG C by lithium hydroxide tune pH >=10, heat preservation 1-3h sufficiently reacts.
Preferably, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 1) is to anti-
It answers and lithium hydroxide is added in mother liquor to pH >=11.
Preferably, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 1) will be anti-
Mother liquor is answered to be heated to 80-90 DEG C.
Further, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 2) exists
After first sediment is mixed with phosphoric acid solution, it is heated with stirring to 40-80 DEG C, 1-10h is kept the temperature, sufficiently reacts.
Preferably, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 2) stirring
It is heated to temperature 60 C.
Preferably, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 2) is described
In phosphoric acid solution: water/the first sediment=12ml/g；Phosphoric acid amount, which is more than or equal to, reacts required theoretical molar amount with sediment
1.05 again.In step reaction, water consumption excessively can increase cost because rectifying cost improves, and water consumption is very few and cannot fill
Divide dissolution, it is therefore preferable that water/first sediment=12ml/g.
Preferably, in circulation and stress hydro-thermal method reaction mother liquor of the present invention in the method for remaining lithium, the separation solid-liquid
Method includes but is not limited to the modes such as to filter, be centrifuged.
Preferably, in above-mentioned circulation and stress hydro-thermal legal system electrode material reaction mother liquor remaining lithium method, step 3) separation
It is used as the raw material of hydro-thermal legal system electrode material after remaining solvent is concentrated after lithium sulfate aqueous solution.
Electrode material of the present invention is phosphate metal lithium salt electrode material, including but not limited to LiFePO4, cobalt phosphate
Lithium, LiNiPO, iron manganese phosphate for lithium, lithium manganese phosphate etc..
In the step 1) of method of the invention, a small amount of metal cation (Fe present in lithium hydroxide and reaction mother liquor
Ion, Mn ion, Co ion etc. it is one or more) and anion (phosphate anion) reaction generate sediment, sediment packet
Include alkali (iron hydroxide, manganous hydroxide, cobalt hydroxide etc. one or more) and salt (lithium phosphate, one hydrogen of phosphoric acid, two lithium).Through step
No longer containing the other impurities metal ion and phosphorus other than lithium ion in the first isolated clear solution after rapid 1) processing
Acid ion.
It is about 10% by elemental lithium content in step 1) treated the first sediment, since lithium is worth higher, needs pair
Elemental lithium is sufficiently recycled in first sediment.In first sediment elemental lithium mainly with lithium phosphate, one hydrogen of phosphoric acid, two lithium with
And lithium sulfate these types mode that a small amount of wet part is brought into exists.After the processing of step 2) phosphoric acid solution, in the second sediment no longer
Containing elemental lithium.Second clear solution main component is phosphoric acid, lithium dihydrogen phosphate, can be directly used as the original of hydro-thermal legal system electrode material
Material.
It is lithium sulfate by solute main component in step 1) treated the first clear solution, solvent main component is water
Or the molten object altogether of organic solvent (ethylene glycol, acetone etc. one or more) or water and organic solvent.First clear solution with from
Proton exchange (including Bipolar Membrane) recycles elemental lithium, and concentrated solvent obtained in removal process also can be recycled, and continues to serve as
Hydro-thermal method prepares the solvent of olivine structural electrode material, realizes sufficiently recycling for reaction mother liquor all material.And it should
Removal process has prevented the introducing of new impurity without adding new raw material.Organic solvent does not lose, and will not cause not to environment
Good influence.Meanwhile the method cyclicity is good, the rate of recovery is high, preparation section is simple, control difficulty is low, energy consumption is small, has both fabulous
Circulation and stress effect and very high cost performance.
The beneficial effects of the present invention are:
1, method of the invention, reaction mother liquor, which can be, prepares various phosphate metal lithium salts, such as LiFePO4, cobalt phosphate
The mother liquor of the electrode materials such as lithium, LiNiPO, iron manganese phosphate for lithium, lithium manganese phosphate, it is applied widely.
2, using the remaining lithium in recyclable method high efficiente callback hydro-thermal legal system electrode material reaction mother liquor, from solid-liquid two-phase
In sufficiently extract elemental lithium, no waste, solution is also recycled, significantly reduce hydro-thermal method technique production (raw material) at
This, is conducive to large-scale promotion application of the hydro-thermal method technique in industrialized production.
3, new raw material, new element are not added, and circulation and stress effect is good, and process is simple, cost performance is high.
Detailed description of the invention
Fig. 1 is the XRD diagram for the ferric phosphate that embodiment 1 obtains.
Specific embodiment
It is illustrated below by way of specific embodiment is further to summary of the invention of the invention, but should not be construed as the present invention
Range be only limitted to example below, invention thinking according to the present invention and entire contents, can will be each in following instance
Technical characteristic makes combination/replacement/adjustment/modification appropriate etc., this is will be obvious to those skilled in the art that still
Belong to the scope that the present invention protects.
Embodiment 1
Water intaking thermal method prepares the reaction mother liquor of LiFePO4, is warming up to 80 DEG C, and lithium hydroxide is added, and adjusts pH value and is greater than
11,2h is kept the temperature, lithium phosphate and ferric hydroxide precipitate suspended matter are formed；It is centrifugated solid-liquid, respectively obtains solid sediment and clear
Clear solution.
Solid sediment is added in phosphoric acid, temperature 60 C, 5g precipitating plus 60mL water, it is anti-with sediment for adding phosphoric acid amount
1.05 times for answering theoretical molar value.Insulation reaction 2 hours, the ferric phosphate precipitating of white is obtained, XRD diagram is shown in Fig. 1, is centrifugated
The mixing clear solution for obtaining lithium dihydrogen phosphate and phosphoric acid, other industrial chemicals are not added, do not have to removal of impurities, and purity is high can be used as
Hydro-thermal method produces the raw material of LiFePO4, the rate of recovery > 95% of lithium in sediment.
Clear solution is put into homogeneous film device (20 groups of films), electrodialysis is carried out with voltage 16V constant pressure, separates lithium sulfate
And reuse is concentrated in ethylene glycol, organic solvent.Obtain lithium sulfate aqueous solution.The recovery efficiency > 98% of ethylene glycol.
Lithium sulfate aqueous solution is put into bipolar membrane device (7 groups of films), voltage 24V constant pressure carries out electrolysis and electrodialysis, by sulphur
Sour lithium is separated into lithium hydroxide and sulfuric acid.Lithium hydroxide can be used as the raw material reuse of hydro-thermal method production LiFePO4, and sulfuric acid can be made
For byproduct.The rate of recovery > 98% of lithium in electrode film.
Embodiment 2
Lithium manganese phosphate mother liquor is taken, is warming up to 60 DEG C, lithium hydroxide is added, pH value is adjusted and is greater than 11, keep the temperature 3h, form phosphoric acid
Lithium and manganous hydroxide precipitate suspended matter；It is centrifugated solid-liquid, respectively obtains solid sediment and clear solution.
Solid sediment is added in phosphoric acid solution, 40 DEG C of temperature, 5g precipitating plus 60mL water, add phosphoric acid amount be and precipitating
1.05 times of object reaction theory mole value.Insulation reaction 10 hours, the manganese phosphate precipitating of white is obtained, centrifuge separation obtains phosphoric acid
The mixing clear solution of dihydro lithium and phosphoric acid can be used as the raw material of hydro-thermal method production lithium manganese phosphate.The rate of recovery of lithium in sediment
> 95%.
By clear solution be put into homogeneous film device (20 groups of films) voltage 16V constant pressure carry out electrodialysis, separation lithium sulfate and
Reuse is concentrated in ethylene glycol, organic solvent.Obtain lithium sulfate aqueous solution.The recovery efficiency > 98% of ethylene glycol.
Lithium sulfate aqueous solution is put into bipolar membrane device (7 groups of films), voltage 24V constant pressure carries out electrolysis and electrodialysis, by sulphur
Sour lithium is separated into lithium hydroxide and sulfuric acid.Lithium hydroxide can be used as the raw material reuse of hydro-thermal method production lithium manganese phosphate, and sulfuric acid can be made
For byproduct.The rate of recovery > 98% of lithium in electrode film.
Embodiment 3
Iron manganese phosphate for lithium mother liquor is taken, is warming up to 100 DEG C, lithium hydroxide is added, pH value is adjusted and is greater than 10, keep the temperature 1h, formed
Lithium phosphate, manganous hydroxide and ferric hydroxide precipitate suspended matter；It is centrifugated solid-liquid, respectively obtain solid sediment and is clarified molten
Liquid.
Solid sediment is added in phosphoric acid, 80 DEG C of temperature, 5g precipitating plus 60mL water, it is anti-with sediment for adding phosphoric acid amount
1.05 times for answering theoretical molar value.Insulation reaction 1.5 hours, the manganese phosphate and ferric phosphate precipitating, centrifuge separation for obtaining white obtained
The mixing clear solution for obtaining lithium dihydrogen phosphate and phosphoric acid can be used as the raw material of hydro-thermal method production iron manganese phosphate for lithium.Lithium in sediment
Rate of recovery > 95%.
By clear solution be put into homogeneous film device (20 groups of films) voltage 16V constant pressure carry out electrodialysis, separation lithium sulfate and
Reuse is concentrated in ethylene glycol, organic solvent.Obtain lithium sulfate aqueous solution.The recovery efficiency > 98% of ethylene glycol.
Lithium sulfate aqueous solution is put into bipolar membrane device (7 groups of films), voltage 24V constant pressure carries out electrolysis and electrodialysis, by sulphur
Sour lithium is separated into lithium hydroxide and sulfuric acid.Lithium hydroxide can be used as the raw material reuse of hydro-thermal method production lithium ferric manganese phosphate, and sulfuric acid can
As byproduct.The rate of recovery > 98% of lithium in electrode film.
Embodiment 4
Cobalt phosphate lithium mother liquor is taken, is warming up to 80 DEG C, lithium hydroxide is added, pH value is adjusted and is greater than 11, keep the temperature 2h, form phosphoric acid
Lithium and cobalt hydroxide precipitate suspended matter；It is centrifugated solid-liquid, respectively obtains solid sediment and clear solution.
Solid sediment is added in phosphoric acid, i.e. temperature 60 C, 5g precipitating plus 60mL water, adds the phosphoric acid amount to be and sediment
1.05 times of reaction theory mole value.Insulation reaction 2 hours, the cobalt phosphate precipitating of white is obtained, centrifuge separation obtains di(2-ethylhexyl)phosphate
The mixing clear solution of hydrogen lithium and phosphoric acid can be used as the raw material of hydro-thermal method production cobalt phosphate lithium.The rate of recovery > of lithium in sediment
95%.
By clear solution be put into homogeneous film device (20 groups of films) voltage 16V constant pressure carry out electrodialysis, separation lithium sulfate and
Reuse is concentrated in ethylene glycol, organic solvent.Obtain lithium sulfate aqueous solution.The recovery efficiency > 98% of ethylene glycol.
Lithium sulfate aqueous solution is put into bipolar membrane device (7 groups of films), voltage 24V constant pressure carries out electrolysis and electrodialysis, by sulphur
Sour lithium is separated into lithium hydroxide and sulfuric acid.Lithium hydroxide can be used as the raw material reuse of hydro-thermal method production cobalt phosphate lithium, and sulfuric acid can be made
For byproduct.The rate of recovery > 98% of lithium in electrode film.
Comparative example 1
LiFePO4 mother liquor is taken, is warming up to 80 DEG C, lithium hydroxide is added, pH value is adjusted and is greater than 11, keep the temperature 2h, form phosphoric acid
Lithium and ferric hydroxide precipitate suspended matter；It is centrifugated solid-liquid, respectively obtains solid sediment and clear solution.
Solid sediment is added in phosphoric acid, i.e. temperature 60 C, 5g precipitating plus 60mL water, adds the phosphoric acid amount to be and sediment
1.05 times of reaction theory mole value.Insulation reaction 2 hours, the ferric phosphate precipitating of white is obtained, centrifuge separation obtains di(2-ethylhexyl)phosphate
The mixing clear solution of hydrogen lithium and phosphoric acid can be used as the raw material of hydro-thermal method production LiFePO4.
Lithium sulfate solution is increased to 80 DEG C, barium hydroxide is added, reacts 2h, generates barium sulfate and lithium hydroxide,
Separation barium sulfate and lithium hydroxide are cleaned by horizontal spiral centrifuge, needs the cleaning of three-level or more to separate, the solution obtained is
Dilute lithium hydroxide, can be with reuse after concentration.Ba ion 0.2mg/L in the reuse solution of acquisition introduces metal impurities, and of the invention
Metal impurities barium will not be introduced.The blanc fixe of acquisition, which is dried, can be used as byproduct.
The comparative experiments has recycled lithium, the rate of recovery of lithium about 95%, but has introduced by-product barium, and increase barium sulfate
Filtering, cleaning, drying and other steps, hence it is evident that increase production technology, need the production line of a by-product barium sulfate, energy consumption cost
It obviously increases.
Comparative example 2
Take LiFePO4 mother liquor, be warming up to 80 DEG C, lithium hydroxide is added, adjust pH value 8, keep the temperature 2h, formed lithium phosphate and
Ferric hydroxide precipitate suspended matter is centrifugated solid-liquid, respectively obtains solid sediment and clear solution.
Contain Fe ion in clarified solution, Fe ion can destroy the electrode film in Bipolar Membrane, Bipolar Membrane is made to fail.
The comparative experiments is not thorough the Fe ion remaval in mother liquor, makes the electrode membrane lifetime deep fades of Bipolar Membrane, bright
It is aobvious to increase cost.
Claims (10)
1. a kind of method of remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor, which is characterized in that comprising steps of
1) lithium hydroxide is added into hydro-thermal legal system electrode material reaction mother liquor sufficiently to react, then it is clear to obtain first for separation solid-liquid
Clear solution and the first sediment；
2) the first sediment is mixed with phosphoric acid solution, sufficiently after reaction, separation solid-liquid obtains the second clear solution and second and sinks
Second clear solution is used as the raw material of hydro-thermal legal system electrode material by starch；
3) by the first clear solution by amberplex, separation lithium sulfate obtains lithium sulfate aqueous solution；
4) separate lithium ion with sulfate ion by Bipolar Membrane isolated lithium sulfate aqueous solution, and respectively with water
It is electrolysed the hydroxide ion obtained and hydrogen ion combines, respectively obtain lithium hydroxide solution and sulfuric acid solution, lithium hydroxide solution
It is used as the raw material of hydro-thermal legal system electrode material after concentrated.
2. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 1
Sign is that then reaction mother liquor is heated to 60-100 DEG C by step 1) lithium hydroxide tune pH >=10, heat preservation 1-3h is sufficiently anti-
It answers.
3. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 2
Sign is that lithium hydroxide is added into reaction mother liquor to pH >=11 for step 1).
4. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 2
Sign is that reaction mother liquor is heated to 80-90 DEG C by step 1).
5. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 1
Sign is that step 2) is heated with stirring to 40-80 DEG C after the first sediment is mixed with phosphoric acid solution, keeps the temperature 1-10h, sufficiently anti-
It answers.
6. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 5
Sign is that step 2) is heated with stirring to temperature 60 C.
7. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 1
Sign is, in the step 2) phosphoric acid solution: water/the first sediment=12ml/g, and phosphoric acid amount is more than or equal to reacts with sediment
1.05 times of required theoretical molar amount.
8. the method for remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 1, it is special
Sign is that the method for the separation solid-liquid is filtering or centrifugation.
9. the method for remaining lithium, special in circulation and stress hydro-thermal legal system electrode material reaction mother liquor according to claim 1
Sign is that step 3) separates the concentrated rear former material for being used as hydro-thermal legal system electrode material of remaining solvent after lithium sulfate aqueous solution
Material.
10. remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor described in any one according to claim 1~9
Method, which is characterized in that the electrode material be LiFePO4, cobalt phosphate lithium, LiNiPO, iron manganese phosphate for lithium or manganese phosphate
Lithium.
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| CN201811067306.3A CN109295312A (en) | 2018-09-13 | 2018-09-13 | A kind of method of remaining lithium in circulation and stress hydro-thermal legal system electrode material reaction mother liquor |
| CN201910077773.2A CN109504861B (en) | 2018-09-13 | 2019-01-28 | Method for recycling residual lithium in electrode material reaction mother liquor prepared by hydrothermal method |
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| CN112299451A (en) * | 2020-03-25 | 2021-02-02 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine in lithium phosphate form |
| CN116239090A (en) * | 2022-12-30 | 2023-06-09 | 杭州蓝然技术股份有限公司 | Process for preparing phosphoric acid and lithium hydroxide from lithium phosphate |
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| CN115432722A (en) * | 2022-08-31 | 2022-12-06 | 宁波容百新能源科技股份有限公司 | Lithium circulation system and preparation method of positive electrode material precursor |
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| EP2365867A4 (en) * | 2008-11-17 | 2012-06-06 | Chemetall Foote Corp | Recovery of lithium from aqueous solutions |
| CN102897803B (en) * | 2012-10-22 | 2014-04-16 | 四川天齐锂业股份有限公司 | Method for recycling mother solution generated in lithium iron phosphate preparation based on liquid phase method |
| JP6368374B2 (en) * | 2013-10-23 | 2018-08-01 | ネマスカ リチウム インコーポレーテッド | Method and system for preparing lithium hydroxide |
| CN107298450B (en) * | 2016-08-31 | 2019-11-29 | 江苏力泰锂能科技有限公司 | The method for preparing lithium hydroxide and lithium carbonate using soluble lithium salt solution |
| CN107954460A (en) * | 2016-10-14 | 2018-04-24 | 德阳威旭锂电科技有限责任公司 | A kind of method for preparing high whiteness and high-purity sulfuric acid barium |
| KR101888181B1 (en) * | 2016-12-23 | 2018-08-13 | 주식회사 포스코 | Method for manufacturing lithium hydroxide and lithium carbonate |
| CN107915239A (en) * | 2017-12-08 | 2018-04-17 | 天齐锂业股份有限公司 | A kind of method for recycling hydro-thermal method production LiFePO4 waste liquid and preparing high-purity sulphuric acid lithium |
| CN109850927B (en) * | 2019-03-29 | 2021-04-20 | 四川顺应动力电池材料有限公司 | Method for preparing high-purity lithium hydroxide |
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2018
- 2018-09-13 CN CN201811067306.3A patent/CN109295312A/en not_active Withdrawn
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2019
- 2019-01-28 CN CN201910077773.2A patent/CN109504861B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299451A (en) * | 2020-03-25 | 2021-02-02 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine in lithium phosphate form |
| CN116239090A (en) * | 2022-12-30 | 2023-06-09 | 杭州蓝然技术股份有限公司 | Process for preparing phosphoric acid and lithium hydroxide from lithium phosphate |
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| Publication number | Publication date |
|---|---|
| CN109504861A (en) | 2019-03-22 |
| CN109504861B (en) | 2020-07-28 |
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