CN105609758A - Preparation method of rubdium- and cesium-doped lithium-rich ternary cathode material for lithium-ion battery - Google Patents
Preparation method of rubdium- and cesium-doped lithium-rich ternary cathode material for lithium-ion battery Download PDFInfo
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- CN105609758A CN105609758A CN201610145892.3A CN201610145892A CN105609758A CN 105609758 A CN105609758 A CN 105609758A CN 201610145892 A CN201610145892 A CN 201610145892A CN 105609758 A CN105609758 A CN 105609758A
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Abstract
The invention discloses a preparation method of a rubdium- and cesium-doped lithium-rich ternary cathode material for a lithium-ion battery. The method comprises the following steps: (1) preparing a precursor solution A; (2) preparing a precipitant solution B; (3) preparing a pH value adjusting solution C; (4) simultaneously adding the precursor solution A, the precipitant solution B and the pH value adjusting solution C to water respectively, forming a nickel-manganese-cobalt ternary sediment, and washing, drying, crushing and sieving the sediment; and (5) mixing a lithium salt and a rubdium salt or a cesium salt or a rubdium-cesium mixed salt at the stoichiometric ratio, carrying out ball-milling, drying and sieving in an ethanol medium, carrying out calcination in air, and crushing and sieving the product to obtain a corresponding lithium-rich manganese-based material Li<1.13-x-y>Rb<x>Cs<y>Ni<0.2>Co<0.2>Mn<0.47>O<2>, in which x+y is smaller than or equal to 1.0 and greater than or equal to 0.01. The preparation method achieves equivalent cation doping in a lithium-rich ternary material structure; the lithium-rich ternary cathode material has relatively good ion and electron conductivity, rate capability and cycle lifetime, and is beneficial to improvement of the energy density of the battery; and the synthetic method disclosed by the invention is friendly to environment, simple, feasible, high in yield, good in controllability and suitable for mass production.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery rubidium caesium blended positive pole material, specifically a kind of rubidium caesium elements doped lithium fromThe preparation method of the rich lithium tertiary cathode material of sub-battery.
Background technology
Be extensively only 130Wh/kg as its actual specific energy of ferric phosphate lithium cell of power battery anode material at presentLeft and right, cannot meet the requirement of following electric automobile to energy density, and that lithium-rich manganese-based anode material has higher energy is closeDegree, and higher than the specific discharge capacity of one times of positive electrode current material, cause people's extensive attention, lithium-rich manganese-based material is expected to getIn generation, is the LiFePO4 of the positive strength of public attention on market at present, becomes the main flow of following domestic power lithium-ion battery positive electrode developmentDirection. Wherein rich lithium ion battery positive electrode xLi2MnO3 (1-x) LiMO2(M of layer structure ternary is Mn, Co, Ni)Because of there is height ratio capacity (250mAhg-1), excellent cycle performance and compared with advantages such as low prices by extensive concern, recognizedFor being is hopeful to be applied to one of positive electrode in lithium ion battery of future generation most.
Lithium-rich anode material xLi2MnO3 (1-x), although LiMO2 has higher charge/discharge capacity, also existsProblem, as irreversible capacity is high first, high rate performance is poor, cycle performance is poor etc. Mainly by doping, coated, particle at presentThe measure such as nanometer, synthetic composite material improves its chemical property. Wherein select suitable dopant and doping ratioCan effectively improve the chemical property of material. Common are metal cation doping, metalloid anion doping or zwitterionComposite mixed. Wherein cation equivalent Doping not only contributes to maintain the stability of material structure, and can promote materialIon and electron conduction, thus the overall performance of lithium-rich anode material improved comprehensively.
Summary of the invention
The object of the present invention is to provide the preparation method of the rich lithium tertiary cathode material of a kind of rubidium caesium doped lithium ion battery,To solve the problem proposing in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
A preparation method for the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery, comprises the following steps:
(1) soluble manganese salt, solubility cobalt salt and soluble nickel salt is more molten than formation presoma soluble in water by certain meteringLiquid A;
(2) by the inorganic salts formation precipitant solution soluble in water B of carbonate or formation precipitation;
(3) be equipped with pH value regulator solution C;
(4) precursor solution A, precipitant solution B and pH value regulator solution C are added to the water respectively simultaneously, form nickel and cobalt containing manganeseTernary precipitate and by it washing, oven dry, pulverize and sieve;
(5) will be by metering than mixing lithium salts and rubidium salt or cesium salt or rubidium caesium salt-mixture, ball milling in ethanol medium, oven dry is sieved,Then under atmosphere, calcine, pulverize and sieve, obtain corresponding lithium-rich manganese-based material Li1.13-x-yRbxCsyNi0.2Co0.2Mn0.47O2，0.01≤x+y≤1.0。
As the further scheme of the present invention: the chemical general formula of described rubidium caesium doping ternary lithium-rich anode material isLi1.13-x-yRbxCsyNi0.2Co0.2Mn0.47O2,0.01≤x+y≤1.0, i.e. mol ratio Li:(Rb+Cs wherein)=(0.13-1.12):(0.01-1.0)。
As further scheme of the present invention: described soluble manganese salt is manganese halide, manganese sulfate, manganese acetate or manganese nitrateIn a kind of or two or more; Described solubility cobalt salt be a kind of in halogenation cobalt, cobalt acetate, cobaltous sulfate or cobalt nitrate orTwo or more; Described soluble nickel salt be a kind of in various nickel halogenides, nickel acetate, nickelous sulfate or sodium nitrate or two kinds withUpper, described inorganic salts is a kind of in sodium carbonate, carbonic hydroammonium or for both.
As further scheme of the present invention: described lithium salts is lithium halide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfateOr lithium hydroxide; Described rubidium salt is rubidium halide, rubidium carbonate, acetic acid rubidium, rubidium nitrate or rubidium hydroxide; Described cesium salt is halogenationCaesium, cesium carbonate, cesium acetate, cesium nitrate or cesium hydroxide.
As further scheme of the present invention: total in precursor solution A of manganese, nickel and the cobalt ions in step (1)Concentration is 0.1molL-1～2.5molL-1.
As further scheme of the present invention: the concentration of described precipitant solution B is 0.1molL-1～2.5molL-1。
As further scheme of the present invention: described water is distilled water or deionized water, and described atmosphere is air, oxygenThe mist of gas and nitrogen or oxygen and argon gas, in described mist, the volume percent content of oxygen is 1～40%.
As further scheme of the present invention: described pH value regulator solution C adopts ammoniacal liquor and acetic acid.
As further scheme of the present invention: described precursor solution A and being mixed into slowly of precipitant solution B addEnter, speed is 0.001mLmin-1 ~ 50mLmin-1, and mixed solution mixing speed is 50rpm ~ 1200rpm.
As further scheme of the present invention: described precursor solution A and lithium salts and rubidium salt or cesium salt or rubidium caesium are mixedClose salt after ball milling mixes, sieves, then obtain a kind of rubidium or caesium or rubidium caesium doping ternary lithium-rich anode material, heat place through heat treatmentThe temperature range of reason is 400 ~ 1000oC, and heating rate is 1～20 DEG C of min-1, and temperature retention time is 10min ~ 24h.
Compared with prior art, the invention has the beneficial effects as follows: the present invention adopts the mode of rubidium caesium doping to realize at rich lithiumCation doping of equal value in ternary material structure, compares with traditional rich lithium tertiary cathode material, have better ion andElectron conduction, high rate performance and cycle life, be conducive to improve energy content of battery density; Synthetic method environment provided by the inventionClose friend, simple and easy to do, productive rate is high, and controllability is good, is applicable to large-scale production.
Brief description of the drawings
Fig. 1 is that rubidium synthetic in embodiment 1 adulterates rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2'sStereoscan photograph;
Fig. 2 is that rubidium synthetic in embodiment 1 adulterates rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2'sXRD spectra;
Fig. 3 is that rubidium synthetic in embodiment 1 adulterates rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2'sCyclic voltammetry curve;
Fig. 4 is synthetic without the rubidium rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2 that adulterates in embodiment 1Cyclic voltammetry curve;
Fig. 5 is that rubidium synthetic in embodiment 1 adulterates rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2'sCharging and discharging curve comparison diagram;
Fig. 6 is synthetic without the rubidium rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2 that adulterates in embodiment 1Charging and discharging curve comparison diagram;
Fig. 7 is rubidium synthetic in embodiment 1 doping and without the adulterate high rate performance correlation curve of rich lithium ternary material of rubidium.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly and completelyDescribe, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment. Based on thisEmbodiment in bright, those of ordinary skill in the art are not making the every other enforcement obtaining under creative work prerequisiteExample, all belongs to the scope of protection of the invention.
Embodiment 1
Taking NiSO46H2O, CoSO47H2O, MnSO4H2O as raw material, match well according to the metering of transition metal in productMetal ion total concentration processed is the aqueous solution of 2mol ﹒ L-1, prepares the Na2CO3 solution of 2molL-1 and 2molL-1 simultaneouslyNH4HCO3 solution; Taking a certain amount of deionized water as end liquid, Na2CO3 solution, NH4HCO3 solution, metal ion solution three liquidAnd stream adds in reactor, reaction is precipitated Mn0.54Ni0.23Co0.23CO3; Be precipitated to nothing by deionized water filtering and washingSulfate radical is residual, after product is dried, pulverizes and sieves and obtains Mn0.54Ni0.23Co0.23CO3 presoma; Mix by metering ratioRb2CO3 and Li2CO3, ball milling 2h in ethanol medium, oven dry is sieved, and then under air atmosphere, carries out forging of different temperaturesBurn, pulverize and sieve, obtain the corresponding rubidium rich lithium tertiary cathode material Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2 that adulterates.
Refer to Fig. 1-7, Fig. 1 is the ESEM photograph that embodiment 1 prepares Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2Sheet, Li1.03Rb0.1Ni0.2Co0.2Mn0.47O2 is average grain diameter 2.5m particle, particle is made up of fritter shape unit. XRD(Fig. 2) spectrogram illustrative material has layer structure, is the good rich lithium tertiary cathode material of crystalline form.
The carbon membrane electrode that embodiment 1 is made is assembled half-cell according to following step: by the rich lithium tertiary cathode of preparationMaterial and conductive black, binding agent PVDF in mass ratio 8:1:1 are with slurry and be coated in and in aluminum foil current collector, make positive plate, veryUnder empty condition, the dry 4～12h of 60oC～120oC, then transfers in the glove box that is full of argon gas. Taking metal lithium sheet as to electricityThe utmost point, ENTEKPE perforated membrane is barrier film, the ethylene carbonate of 1mol L-1 lithium hexafluoro phosphate and dimethyl carbonate (volume ratio 1:1) mixed solution is electrolyte, is assembled into CR2016 button cell, in LAND battery test system (the limited public affairs of Wuhan gold promise electronicsDepartment provides) on carry out constant current charge-discharge performance test, and carry out electrochemical property test on CHI660E electrochemical workstation.Can find out that from Electrochemical results the prepared rubidium rich lithium tertiary cathode material that adulterates has very high specific energy and fineCycle performance.
Embodiment 2
Taking NiSO46H2O, CoSO47H2O, MnSO4H2O as raw material, match well according to the metering of transition metal in productMetal ion total concentration processed is the aqueous solution of 2mol ﹒ L-1, prepares the Na2CO3 solution of 2molL-1 and 2molL-1 simultaneouslyNH4HCO3 solution; Taking a certain amount of deionized water as end liquid, Na2CO3 solution, NH4HCO3 solution, metal ion solution three liquidAnd stream adds in reactor, reaction is precipitated Mn0.54Ni0.23Co0.23CO3; Be precipitated to nothing by deionized water filtering and washingSulfate radical is residual, after product is dried, pulverizes and sieves and obtains Mn0.54Ni0.23Co0.23CO3 presoma; Mix by metering ratioCs2CO3 and Li2CO3, ball milling 2h in ethanol medium, oven dry is sieved, and then under air atmosphere, carries out forging of different temperaturesBurn, pulverize and sieve, obtain the corresponding caesium rich lithium tertiary cathode material Li1.03Cs0.1Ni0.2Co0.2Mn0.47O2 that adulterates.
The carbon membrane electrode that embodiment 2 is made is assembled half-cell according to following step: by the rich lithium tertiary cathode of preparationMaterial and conductive black, binding agent PVDF in mass ratio 8:1:1 are with slurry and be coated in and in aluminum foil current collector, make positive plate, veryUnder empty condition, the dry 4～12h of 60oC～120oC, then transfers in the glove box that is full of argon gas. Taking metal lithium sheet as to electricityThe utmost point, ENTEKPE perforated membrane is barrier film, the ethylene carbonate of 1mol L-1 lithium hexafluoro phosphate and dimethyl carbonate (volume ratio 1:1) mixed solution is electrolyte, is assembled into CR2016 button cell, in LAND battery test system (the limited public affairs of Wuhan gold promise electronicsDepartment provides) on carry out constant current charge-discharge performance test, and carry out electrochemical property test on CHI660E electrochemical workstation.
Embodiment 3
Taking NiSO46H2O, CoSO47H2O, MnSO4H2O as raw material, match well according to the metering of transition metal in productMetal ion total concentration processed is the aqueous solution of 2mol ﹒ L-1, prepares the Na2CO3 solution of 2molL-1 and 2molL-1 simultaneouslyNH4HCO3 solution; Taking a certain amount of deionized water as end liquid, Na2CO3 solution, NH4HCO3 solution, metal ion solution three liquidAnd stream adds in reactor, reaction is precipitated Mn0.54Ni0.23Co0.23CO3; Be precipitated to nothing by deionized water filtering and washingSulfate radical is residual, after product is dried, pulverizes and sieves and obtains Mn0.54Ni0.23Co0.23CO3 presoma; Mix by metering ratioRb2CO3, Cs2CO3 and Li2CO3, ball milling 2h in ethanol medium, oven dry is sieved, and then under air atmosphere, carries out not equality of temperatureThe calcining of degree, pulverizes and sieves, and obtains the corresponding rubidium caesium rich lithium tertiary cathode material that adulteratesLi1.03Rb0.05Cs0.05Ni0.2Co0.2Mn0.47O2。
The carbon membrane electrode that embodiment 3 is made is assembled half-cell according to following step: by the richness of the rubidium caesium doping of preparationLithium tertiary cathode material and conductive black, binding agent PVDF in mass ratio 8:1:1 are with slurry and be coated in aluminum foil current collector and makePositive plate, under vacuum condition, the dry 4～12h of 60oC～120oC, then transfers in the glove box that is full of argon gas. With metalLithium sheet is to electrode, and ENTEKPE perforated membrane is barrier film, ethylene carbonate and the dimethyl carbonate of 1mol L-1 lithium hexafluoro phosphate(volume ratio 1:1) mixed solution is electrolyte, is assembled into CR2016 button cell, in (the Wuhan gold promise of LAND battery test systemElectronics Co., Ltd. provides) on carry out constant current charge-discharge performance test, and carry out electrochemistry on CHI660E electrochemical workstationPerformance test.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, Er QieDo not deviate from the situation of spirit of the present invention or essential characteristic, can realize the present invention with other concrete form. Therefore, no matterFrom which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is by appended powerProfit requires instead of above-mentioned explanation limits, and is therefore intended to drop on all in the implication that is equal to important document of claim and scopeChange and include in the present invention. Any Reference numeral in claim should be considered as limiting related claim.
In addition although should be appreciated that this description is described according to embodiment, be not that each embodiment only wraps,Contain an independently technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art shouldDescription is done as a whole, the technical scheme in each embodiment also can be through appropriately combined, forms those skilled in the artUnderstandable other embodiments.
Claims (10)
1. a preparation method for the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery, is characterized in that, comprises following stepRapid:
(1) soluble manganese salt, solubility cobalt salt and soluble nickel salt is more molten than formation presoma soluble in water by certain meteringLiquid A;
(2) by the inorganic salts formation precipitant solution soluble in water B of carbonate or formation precipitation;
(3) be equipped with pH value regulator solution C;
(4) precursor solution A, precipitant solution B and pH value regulator solution C are added to the water respectively simultaneously, form nickel and cobalt containing manganeseTernary precipitate and by it washing, oven dry, pulverize and sieve;
(5) will be by metering than mixing lithium salts and rubidium salt or cesium salt or rubidium caesium salt-mixture, ball milling in ethanol medium, oven dry is sieved,Then under atmosphere, calcine, pulverize and sieve, obtain corresponding lithium-rich manganese-based material Li1.13-x-yRbxCsyNi0.2Co0.2Mn0.47O2，0.01≤x+y≤1.0。
2. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, the chemical general formula of described rubidium caesium doping ternary lithium-rich anode material is Li1.13-x-YRbxCsyNi0.2Co0.2Mn0.47O2,0.01≤x+y≤1.0, i.e. mol ratio Li:(Rb+Cs wherein)=(0.13-1.12):(0.01-1.0)。
3. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described soluble manganese salt is a kind of or two or more in manganese halide, manganese sulfate, manganese acetate or manganese nitrate; Described canDissolubility cobalt salt is a kind of or two or more in halogenation cobalt, cobalt acetate, cobaltous sulfate or cobalt nitrate; Described soluble nickel salt is eachOne in kind nickel halogenide, nickel acetate, nickelous sulfate or sodium nitrate or two or more, described inorganic salts is sodium carbonate, carbonIn acid hydrogen ammonium a kind of or both.
4. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described lithium salts is lithium halide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate or lithium hydroxide; Described rubidium salt be rubidium halide,Rubidium carbonate, acetic acid rubidium, rubidium nitrate or rubidium hydroxide; Described cesium salt is caesium halide, cesium carbonate, cesium acetate, cesium nitrate or hydrogenCesium oxide.
5. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, the total concentration of manganese, nickel and the cobalt ions in step (1) in precursor solution A is 0.1molL-1～2.5molL-1。
6. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, the concentration of described precipitant solution B is 0.1molL-1～2.5molL-1.
7. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described water is distilled water or deionized water, and described atmosphere is the gaseous mixture of air, oxygen and nitrogen or oxygen and argon gasBody, in described mist, the volume percent content of oxygen is 1～40%.
8. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described pH value regulator solution C adopts ammoniacal liquor and acetic acid.
9. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described precursor solution A and being mixed into slowly of precipitant solution B add, and speed is 0.001mLmin-1 ~ 50mLMin-1, mixed solution mixing speed is 50rpm ~ 1200rpm.
10. the preparation method of the rich lithium tertiary cathode material of rubidium caesium doped lithium ion battery according to claim 1, its featureBe, described precursor solution A and lithium salts and rubidium salt or cesium salt or rubidium caesium salt-mixture are after ball milling mixes, sieves, then through heatProcessing obtains a kind of rubidium or caesium or rubidium caesium doping ternary lithium-rich anode material, and heat treated temperature range is 400 ~ 1000oC, risesTemperature speed is 1～20 DEG C of min-1, and temperature retention time is 10min ~ 24h.
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| CN106981651A (en) * | 2017-05-15 | 2017-07-25 | 上海交通大学 | Rubidium and/or the tertiary cathode material and preparation method, lithium ion battery of caesium doping |
| CN109786736A (en) * | 2018-12-28 | 2019-05-21 | 中南大学 | A kind of nickel cobalt rubidium manganate lithium material and its preparation method and application |
| CN109802111A (en) * | 2018-12-28 | 2019-05-24 | 中南大学 | A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application |
| CN109817919A (en) * | 2019-01-22 | 2019-05-28 | 上海应用技术大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping |
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| CN111952566A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | Rubidium-doped high-rate lithium battery positive electrode material and preparation method thereof |
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| WO2024146478A1 (en) * | 2023-01-05 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method therefor, cathode electrode sheet, electrode assembly, battery, and electrical device |
| CN117101599B (en) * | 2023-08-04 | 2024-10-22 | 香港中文大学（深圳） | Lithium ion sieve adsorbent material and preparation method and application thereof |
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2016
- 2016-03-15 CN CN201610145892.3A patent/CN105609758A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981651A (en) * | 2017-05-15 | 2017-07-25 | 上海交通大学 | Rubidium and/or the tertiary cathode material and preparation method, lithium ion battery of caesium doping |
| CN109786736A (en) * | 2018-12-28 | 2019-05-21 | 中南大学 | A kind of nickel cobalt rubidium manganate lithium material and its preparation method and application |
| CN109802111A (en) * | 2018-12-28 | 2019-05-24 | 中南大学 | A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application |
| CN109817919A (en) * | 2019-01-22 | 2019-05-28 | 上海应用技术大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping |
| CN110797527A (en) * | 2019-10-23 | 2020-02-14 | 昆明理工大学 | Modified lithium-rich manganese-based oxide cathode material and preparation method thereof |
| CN111952566A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | Rubidium-doped high-rate lithium battery positive electrode material and preparation method thereof |
| CN111952585A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof |
| CN112652817A (en) * | 2021-01-04 | 2021-04-13 | 吴翠云 | Lithium ion battery electrolyte and lithium ion battery |
| CN113764671A (en) * | 2021-09-06 | 2021-12-07 | 贵州理工学院 | Anode material of lithium ion battery |
| WO2024146478A1 (en) * | 2023-01-05 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method therefor, cathode electrode sheet, electrode assembly, battery, and electrical device |
| CN117101599A (en) * | 2023-08-04 | 2023-11-24 | 香港中文大学（深圳） | Lithium ion sieve adsorbent material and preparation method and application thereof |
| CN117101599B (en) * | 2023-08-04 | 2024-10-22 | 香港中文大学（深圳） | Lithium ion sieve adsorbent material and preparation method and application thereof |
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