CN108598465A - A method of it extracting lithium from salt lake bittern and prepares anode material of lithium battery - Google Patents

A method of it extracting lithium from salt lake bittern and prepares anode material of lithium battery Download PDF

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CN108598465A
CN108598465A CN201810367740.7A CN201810367740A CN108598465A CN 108598465 A CN108598465 A CN 108598465A CN 201810367740 A CN201810367740 A CN 201810367740A CN 108598465 A CN108598465 A CN 108598465A
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lithium
electrolyte
salt lake
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lake bittern
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陈庆
曾军堂
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Chengdu New Keli Chemical Science Co Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to extracting lithium from salt lake bittern to prepare the preparation method of anode material of lithium battery, salt lake raw water is subjected to secondary nanofiltration filtering, is filtered for the first time, calcium ion, sodium ion, chlorion of the removal ionic diameter in 0.1nm；Second of filtering intercepts lithium ion, magnesium ion of the ionic diameter in 0.072 0.076nm；The magnesium lithium concentrate of interception is dried, is then dispersed in lithium battery conventional electrolysis liquid, high concentration electrolyte is formed；Nickle cobalt lithium manganate crystal is taken off into lithium, quickly adsorbs lithium in the electrolytic solution under potential effect, dry, firing obtains nickle cobalt lithium manganate ternary electrode material.Nickle cobalt lithium manganate crystal is taken off lithium as adsorbent by the present invention, is not only inhaled lithium and is stablized, and directly as positive electrode, without taking off lithium again, the problem of avoiding repeatedly de- lithium molten damage, simplifies the extraction of lithium and use process, collect lithium extraction with applied to one, realizes the efficient utilization of lithium.

Description

A method of it extracting lithium from salt lake bittern and prepares anode material of lithium battery
Technical field
The present invention relates to electrode material of lithium battery technical fields, and in particular to extracts lithium from salt lake bittern and prepares lithium battery Positive electrode and preparation method.
Background technology
Lithium ion battery and traditional accumulator are comparatively, not only energy higher, and discharge capability is stronger, and cycle life is more It is long, and its energy storage efficiency can be more than 90%, and the above feature determines lithium ion battery in sides such as electric vehicle, storage power supplys The great development prospect in face.Determine that the key of lithium-ion-power cell cost and performance is material, the material of lithium-ion-power cell Material determines the development course and operational mode of electric vehicle.Therefore, the bottleneck problem of lithium-ion-power cell is broken through, key exists In the solution of problem of materials.
Current commercialized lithium ion battery mainly uses LiCoO2 as positive electrode at present, but LiCoO2 has safety Property and overcharge resistance performance problem, Co belong to scarce resource, expensive, and metallic cobalt is easy to pollute the environment.And LiNiO2 Stability it is poor, easily cause safety problem, need to be synthesized under oxygen atmosphere, and be easy to happen cationic mixing and generate it is non- Stoichiometric ratio structural compounds.LiMn2O4 is easy to happen the dissolving of crystal transfer and manganese ion in cyclic process, causes Battery capacity decays.Nickle cobalt lithium manganate（LiNixCoyMn1-x-yO2）It is the ternary battery material of current most mainstream, is recognized as It is the development trend in future.Its using cobalt salt, manganese salt, nickel salt as raw material, by allocate cobalt, manganese, nickel three ratio, to obtain not Same electrode characteristic.Nickelic ternary material due to nickel element ratio raising, from 333,532, to 622,711 to 811（Nickel, cobalt, The ratio of manganese three）, there is the advantage of bigger on than energy, cryogenic property, multiplying power discharging property.In recent years with the throwing of research and development Enter, nickelic ternary material oneself become one of the emphasis of battery industry development.
Currently, that there is also processing performances is bad for nickelic tertiary cathode material, there are irreversible reaction, high temperature cyclic performance is poor The problems such as.Since Li+ and Ni2+ radiuses are close, Ni2+ is easy to occupy Li+, causes ion mixing, cause active lithium reduce and Capacity reduces, and the residual lithium of pH value and surface is higher, influences material processing performance, it is difficult to and slurry coating.It under the high temperature conditions, can be by HF Deng corrosion, interfacial structure is destroyed, and then leads to the dissolving of W metal, Co, Mn in the electrolytic solution, causes the decaying of capacity.
Mainstream electric vehicle is all using lithium battery as driving battery on the market at present, and therefore, sufficient lithium resource is for new The development of energy automobile industry is most important.The lithium of early stage is extracted from containing lithium ore, but with the day containing lithium ore Benefit is reduced, and grade is gradually reduced, and salt lake lithium becomes main lithium resource.
Although on reserves, China salt lake lithium has some superiority, unsatisfactory in the water quality of salt lake, except west The Li contents for hiding Salt Lake Zabuye are higher, and Mg/Li is relatively low outer, and not only Li contents are low for Qinghai Salt Lake water, and Mg/Li bits It is not high, cause many difficulties to extraction lithium.Especially there is also many technology barriers from salt lake refinement lithium for low-coat scale.
Prior art personnel utilize inorganic adsorbent selective absorption lithium from salt lake saline at present, and it is high to breach Mg/Li ratio Technical bottleneck, but in practice, stripping liquid lithium concentration is still relatively low, thus it is follow-up need complicated infiltration film process, lithium is carried out it is dense Contracting processing, reprecipitation lithium carbonate etc..Cumbersome, and adsorbent repeatedly recycle it is molten damage it is larger, cause refine lithium cost increase.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide extract lithium from salt lake bittern to prepare lithium battery just The method of pole material solves the molten loss rate height of existing adsorbent, the high defect of adsorbent cost.
The purpose of the present invention is achieved through the following technical solutions：
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
For S1 by salt lake bittern by first layer NF membrane, removal calcium ion, sodium ion, chlorion filter first time nanofiltration Filtrate intercepts lithium ion, magnesium ion, the filtrate of removal second of nanofiltration filtering by second layer NF membrane；
S2 dries the magnesium lithium concentrate intercepted in S1 steps, and it is powder that crushing in pulverizer, which is added, and powder is melted by machinery Collaboration, which unites to be dispersed in the electrolyte of lithium battery, forms high concentration electrolyte；
S3 by nickle cobalt lithium manganate crystal by electrolysis take off lithium after, in S2 step middle and high concentration electrolyte, Carbon anode structure, diaphragm Deng at cell reaction group, the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, further, dry, burn System, obtains nickle cobalt lithium manganate ternary electrode material.
It is filtered by secondary nanofiltration, the magnesium lithium in salt lake bittern is made to concentrate and removes the impurity such as other sodium, calcium, boron, utilized Prefabricated nickle cobalt lithium manganate takes off the lithium vacancy absorption lithium after lithium, cobalt manganic acid lithium ternary electrode material is directly obtained, to effectively make magnesium Lithium detaches.And nickle cobalt lithium manganate crystal is taken off lithium as adsorbent by the present invention, is not only inhaled lithium and is stablized, and directly as anode Material the problem of avoiding repeatedly de- lithium molten damage, simplifies the extraction of lithium and uses process without taking off lithium again, collection lithium extraction With applied to one, the efficient utilization of lithium is realized.
Further, the aperture of first layer NF membrane is 0.08nm in the S1 steps, and the aperture of second layer NF membrane is 0.06nm。
Nanofiltration be between ultrafiltration and it is reverse osmosis between a kind of membrane separation technique, model of the molecular cut off in 80-1000 In enclosing, aperture is several nanometers, therefore claims nanofiltration.The membrane material of nanofiltration has good film forming, thermal stability, chemical stabilization Property, high mechanical strength, acid and alkali-resistance and microbial attack, chlorine-resistant and other oxidizing substances, have high water flux and high salt rejection rate, Anticol body and suspended solid pollutant, Nader's film that is cheap, using at present are mostly aromatic series and the compound Nader's film of polyacids hydrogen species.It is right In composite membrane, the optimization of material and structure, availability can be carried out respectively to the epidermis and supporting layer for playing centrifugation Excellent composite membrane.The form of membrane module has doughnut, rolling, plate and frame and tubular type etc..Wherein, doughnut and rolled film The packed density of component is high, low cost, and hydrodynamic conditions are good in component；But the manufacturing technology of both membrane modules requirement Height, sealing is difficult, and contamination resistance is poor in use, high to feed liquid pre-processing requirements.Although and plate and frame and tubular membrane component are clear Convenience, anti-pollution are washed, but the packed density of film is low, cost is high.Therefore, hollow fiber form or rolling are used in nanofiltration system more Membrane module.
Further, drying temperature is 90-110 DEG C, drying time 2-3h in the S2 steps, the grain size of powder >= 200 mesh.It is dried after concentration, drying temperature is high, and drying time is short, is conducive to later stage crushing drying.
Further, the concrete operations of mechanofusion system are in the S2 steps：Powder and electrolyte are placed together In rotating container, reinforces pressure and shearing, powder and electrolyte adhere to each other, form high concentration electrolyte.
Further, the mass ratio of powder and electrolyte is 1 in the S2 steps：（2.0-3.0）；The high concentration electrolysis Lithium ion mass concentration is 50-70% in liquid.
For the conventional electrolysis liquid of traditional lithium battery, in lithium ion battery, the operating voltage of battery is typically up to 3 ~ 4V, traditional aqueous solution are no longer applicable in, it is therefore necessary to use electrolyte of the non-aqueous solution electrolysis liquid system as lithium ion battery.Its Middle non-aqueous organic solvent is the bulk composition of electrolyte.
Further, the mass ratio of powder and electrolyte is 1 in the S2 steps：2.0；Lithium in the high concentration electrolyte Mass of ion a concentration of 65%.
Further, the solvent of the electrolyte is one kind in cyclic carbonate, linear carbonate or carboxylate, lithium salts For lithium hexafluoro phosphate, lithium perchlorate or LiBF4；The pressure is 1.5-2MPa.
Further, the general formula of nickle cobalt lithium manganate ternary electrode material is LiNi in the S3 stepsxCoyM1-x-yO2Work Property material, wherein x>0 .6, y<0 .4, x+y<1.
The beneficial effects of the invention are as follows：It is filtered by secondary nanofiltration, the magnesium lithium in salt lake bittern is made to concentrate and remove other The impurity such as sodium, calcium, boron after nickle cobalt lithium manganate crystal takes off lithium, have excellent lithium vacancy, after taking off lithium using prefabricated nickle cobalt lithium manganate Lithium vacancy adsorb lithium, directly obtain cobalt manganic acid lithium ternary electrode material.Adsorbent absorption once obtains anode material of lithium battery, Without taking off lithium again, the problem of avoiding repeatedly de- lithium molten damage, simplifies the extraction of lithium and use process, the extraction of collection lithium and application In one, the efficient utilization of lithium is realized.
Specific implementation mode
Technical scheme of the present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is not It is confined to as described below.
Embodiment 1
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
Salt lake bittern is passed through the first layer NF membrane of aperture 0.08nm, removal calcium ion, sodium ion, chlorion, by first by S1 The filtrate of secondary nanofiltration filtering intercepts lithium ion, magnesium ion, removes second of nanofiltration by the second layer NF membrane of aperture 0.06nm The filtrate of filtering；
S2 dry 3h at a temperature of 90 DEG C by the magnesium lithium concentrate intercepted in S1 steps, be added in pulverizer be crushed to grain size >= The powder of 1 parts by weight is dispersed in the electrolyte of the lithium battery of 2.0 parts by weight by mechanofusion system and forms height by 200 mesh Concentration electrolytic solution；
After nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis, battery is constituted with S2 step middle and high concentrations electrolyte, Carbon anode Group, the crystal after de- lithium can adsorb lithium under potential effect, to detach lithium with magnesium, obtain nickel cobalt manganese in the electrolytic solution Sour lithium ternary electrode material.
Specifically, in the S2 steps；Lithium ion mass concentration is 50% in the high concentration electrolyte.
Specifically, the electrolyte solvent is lithium hexafluoro phosphate cyclic carbonate, and lithium salts is lithium hexafluoro phosphate, mass concentration It is 3%.The pressure is 1.5MPa.
The nickle cobalt lithium manganate ternary electrode material wherein obtained is LiNi0.7Co0.1M0.2O2, by cell positive material and gather Vinylidene fluoride in mass ratio 9:1 mixing, is ground into slurry, is coated on aluminium foil, is dried in 60 DEG C of vacuum drying chambers for 24 hours, It takes out, is cut into electrode film, you can obtain positive plate of lithium battery；Positive plate prepared by method described above is anode, is pressed from upper past Lower sequence is put into the lithium battery of gasket, electrolyte, diaphragm and the manufacture of metal lithium sheet cathode, the lithium battery of manufacture, in voltage 3.50 V, under the conditions of the charge and discharge of 100 mA/g, discharge capacity is up to 218 mAh/g for the first time, and capacity remains at 163 after 200 cycles MAh/g or so, capacity retention ratio >=83%, coulombic efficiency >=90%.For this purpose, being detached through the invention using crystalline lithium suction lithium is taken off Lithium and magnesium can preferably make lithium insertion lithium vacancy, obtained electrode material have basic positive electrode performance.If into one Step improves the stability of cobalt manganic acid lithium ternary electrode material, and well known routine techniques may be used and be further processed to the material, It is fully able to reach batch requirement.
Embodiment 2
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
Salt lake bittern is passed through the first layer NF membrane of aperture 0.08nm, removal calcium ion, sodium ion, chlorion, by first by S1 The filtrate of secondary nanofiltration filtering intercepts lithium ion, magnesium ion, removes second of nanofiltration by the second layer NF membrane of aperture 0.06nm The filtrate of filtering；
S2 dry 2.5h at a temperature of 100 DEG C by the magnesium lithium concentrate intercepted in S1 steps, are added in pulverizer and are crushed to grain The powder of 1 parts by weight, is dispersed in shape in the electrolyte of the lithium battery of 2.5 parts by weight by the mesh of diameter >=200 by mechanofusion system At high concentration electrolyte；
After nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis, battery is formed with S2 step middle and high concentrations electrolyte, Carbon anode Group, the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, and dry, 700 DEG C of firings, 1 hour stabilization obtains To nickle cobalt lithium manganate ternary electrode material.
Specifically, in the S2 steps；Lithium ion mass concentration is 60% in the high concentration electrolyte.
Specifically, the solvent of the electrolyte is cyclic carbonate, linear carbonate and carboxylate composition, and lithium salts is hexafluoro Lithium phosphate, mass concentration 2%；Lower prefabricated lithium concentration can obtain and more refine lithium dispersion in the electrolytic solution.The pressure Power is 1.8MPa, and the lithium of separation, magnesium is preferably made to be scattered in electrolyte, in order to which crystal is subsequently inhaling lithium.
After S2 step middle and high concentration electrolyte adsorbs 30min by the crystal after taking off lithium under potential effect, Mg/Li ratio 1.2 are reduced to by 5.3, adsorptivity of the de- crystalline lithium to lithium is further demonstrated, to make lithium be isolated from magnesium.
Embodiment 3
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
For S1 by salt lake bittern by first layer NF membrane, removal calcium ion, sodium ion, chlorion filter first time nanofiltration Filtrate intercepts lithium ion, magnesium ion, the filtrate of removal second of nanofiltration filtering by second layer NF membrane；
S2 dry 2h at a temperature of 110 DEG C by the magnesium lithium concentrate intercepted in S1 steps, are added in pulverizer and are crushed to grain size The powder of 1 parts by weight is dispersed in the electrolyte of the lithium battery of 3.0 parts by weight by mechanofusion system and is formed by >=200 mesh High concentration electrolyte；
After nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis, battery is constituted with S2 step middle and high concentrations electrolyte, Carbon anode Group, the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, dry, fire 1h for 700 DEG C and obtain nickel cobalt manganese Sour lithium ternary electrode material.
Specifically, in the S2 steps；Lithium ion mass concentration is 70% in the high concentration electrolyte.
Specifically, the solvent of the electrolyte is cyclic carbonate, and lithium salts is lithium perchlorate, mass concentration 1%；It is described Pressure is 2.0MPa.
Embodiment 4
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
Salt lake bittern is passed through the first layer NF membrane of aperture 0.08nm, removal calcium ion, sodium ion, chlorion, by first by S1 The filtrate of secondary nanofiltration filtering intercepts lithium ion, magnesium ion, removes second of nanofiltration by the second layer NF membrane of aperture 0.06nm The filtrate of filtering；
S2 dry 2.5h at a temperature of 95 DEG C by the magnesium lithium concentrate intercepted in S1 steps, are added in pulverizer and are crushed to grain size The powder of 1 parts by weight is dispersed in the electrolyte of the lithium battery of 2.0 parts by weight by mechanofusion system and is formed by >=200 mesh High concentration electrolyte；
After nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis, with the groups such as S2 step middle and high concentrations electrolyte, Carbon anode, diaphragm Battery pack, the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, dry, and 1 h is fired at 750 DEG C, is obtained To nickle cobalt lithium manganate ternary electrode material.
Specifically, in the S2 steps；Lithium ion mass concentration is 65% in the high concentration electrolyte.
Specifically, the solvent of the electrolyte is cyclic carbonate, and lithium salts is lithium hexafluoro phosphate, mass concentration 1%.Institute It is 1.9MPa to state pressure.
Embodiment 5
The method that lithium prepares anode material of lithium battery is extracted from salt lake bittern, and salt lake bittern is subjected to secondary nanofiltration and is obtained by filtration Magnesium lithium concentrate is dried, and is then dispersed in the electrolyte of lithium battery and is formed high concentration electrolyte；Nickle cobalt lithium manganate crystal is taken off Lithium quickly adsorbs lithium under potential effect, obtains nickle cobalt lithium manganate ternary electrode material in the electrolytic solution；Specifically include following step Suddenly：
For S1 by salt lake bittern by first layer NF membrane, removal calcium ion, sodium ion, chlorion filter first time nanofiltration Filtrate intercepts lithium ion, magnesium ion, the filtrate of removal second of nanofiltration filtering by second layer NF membrane；
S2 dry 2.5h at a temperature of 95 DEG C by the magnesium lithium concentrate intercepted in S1 steps, are added in pulverizer and are crushed to grain size The powder of 1 parts by weight is dispersed in the electrolyte of the lithium battery of 2.0 parts by weight by mechanofusion system and is formed by >=200 mesh High concentration electrolyte；
After nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis, with the groups such as S2 step middle and high concentrations electrolyte, Carbon anode, diaphragm At battery pack, the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, dry, fire, obtain nickel cobalt manganese Sour lithium ternary electrode material.
Specifically, in the S2 steps；Lithium ion mass concentration is 60% in the high concentration electrolyte.
Specifically, the solvent of the electrolyte is cyclic carbonate, and lithium salts is lithium hexafluoro phosphate, mass concentration 1%.Institute It is 1.5MPa to state pressure.
Comparative example 1
Identical as the preparation method for implementing 2, the prefabricated highly concentrated electrolyte of use is also identical.It is logical in S2 step middle and high concentration electrolyte It crosses the crystal after taking off lithium and after absorption 60min, extends 30min, by test, Mg/Li ratio is reduced to by 5.3 under potential effect 0.5, therefore take off crystalline lithium through the invention and adsorb the generation for making essence, and be also effective.It reaches the same goal and extends adsorption time, So that more lithiums are by adsorbing separation.
The above is only a preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein Form is not to be taken as excluding other embodiments, and can be used for other combinations, modifications, and environments, and can be at this In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection domain of appended claims of the present invention It is interior.

Claims (8)

1. extracting the method that lithium prepares anode material of lithium battery from salt lake bittern, which is characterized in that salt lake bittern is carried out two The drying of magnesium lithium concentrate is obtained by filtration in secondary nanofiltration, is then dispersed in the electrolyte of lithium battery and forms high concentration electrolyte；By nickel Cobalt manganic acid lithium crystal takes off lithium, quickly adsorbs lithium in the electrolytic solution under potential effect, obtains nickle cobalt lithium manganate ternary electrode material； Specifically comprise the following steps：
For S1 by salt lake bittern by first layer NF membrane, removal calcium ion, sodium ion, chlorion filter first time nanofiltration Filtrate intercepts lithium ion, magnesium ion, the filtrate of removal second of nanofiltration filtering by second layer NF membrane；
S2 dries the magnesium lithium concentrate intercepted in S1 steps, and it is powder that crushing in pulverizer, which is added, and powder is melted by machinery Collaboration, which unites to be dispersed in the electrolyte of lithium battery, forms high concentration electrolyte；
It is negative with S2 step middle and high concentrations electrolyte, carbon as electrode after nickle cobalt lithium manganate crystal is taken off lithium by S3 by electrolysis Pole, diaphragm etc. constitute battery, and the crystal after de- lithium can adsorb lithium in the electrolytic solution under potential effect, dry, fire To nickle cobalt lithium manganate ternary electrode material.
2. the method according to claim 1 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In the aperture of first layer NF membrane is 0.080nm in the S1 steps, and the aperture of second layer NF membrane is 0.06nm.
3. the method according to claim 1 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In drying temperature is 90-110 DEG C, drying time 2-3h in the S2 steps, the mesh of the grain size of powder >=200.
4. the method according to claim 1 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In, in the S2 steps concrete operations of mechanofusion system be：Powder and electrolyte are placed on together in rotation container, are added Strong pressure and shearing, powder and electrolyte adhere to each other, and form high concentration electrolyte.
5. the method according to claim 4 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In the mass ratio of powder and electrolyte is 1 in the S2 steps：（2.0-3.0）；Lithium ion quality in the high concentration electrolyte A concentration of 50-70%.
6. the method according to claim 5 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In the mass ratio of powder and electrolyte is 1 in the S2 steps：2.0；Lithium ion mass concentration is in the high concentration electrolyte 65%。
7. the method that lithium prepares anode material of lithium battery is extracted from salt lake bittern according to claim 4-6 any one of them, It is characterized in that, the solvent of the electrolyte is one kind in cyclic carbonate, linear carbonate or carboxylate, lithium salts is hexafluoro Lithium phosphate, lithium perchlorate or LiBF4；The pressure is 1.5-2MPa.
8. the method according to claim 1 extracted lithium from salt lake bittern and prepare anode material of lithium battery, feature exist In the general formula of nickle cobalt lithium manganate ternary electrode material is LiNi in the S3 stepsxCoyM1-x-yO2Active material, wherein x>0 .6, y<0 .4, x+y<1.
CN201810367740.7A 2018-04-23 2018-04-23 A method of it extracting lithium from salt lake bittern and prepares anode material of lithium battery Withdrawn CN108598465A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564965A (en) * 2019-06-25 2019-12-13 中南大学 metal lithium alloy and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564965A (en) * 2019-06-25 2019-12-13 中南大学 metal lithium alloy and preparation method and application thereof
CN110564965B (en) * 2019-06-25 2020-09-11 中南大学 Metal lithium alloy and preparation method and application thereof

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