CN113955805A - Lithium-rich cathode material of lithium ion battery and preparation method thereof - Google Patents
Lithium-rich cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 239000010406 cathode material Substances 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000011572 manganese Substances 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 229910009112 xH2O Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 6
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000086 high toxicity Toxicity 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 239000010405 anode material Substances 0.000 description 15
- 229910009055 Li1.2Ni0.2Mn0.6O2 Inorganic materials 0.000 description 13
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009841 combustion method Methods 0.000 description 4
- 229940044658 gallium nitrate Drugs 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 229910001346 0.5Li2MnO3 Inorganic materials 0.000 description 2
- 229910001171 0.5LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910010133 Li2MnO3In Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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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
- H01M4/52—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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
The invention discloses a lithium-rich cathode material of a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving a lithium source material, a nickel source material and a manganese source material in deionized water, and adjusting the pH value to be acidic to form a green transparent solution; adding a gallium source material into the green transparent solution until the gallium source material is completely dissolved, adding a proper amount of absolute ethyl alcohol and polyethylene glycol, and heating in a water bath to obtain a green gelatinous solid; burning and grinding the green gelatinous solid to obtain a black powder precursor; and calcining the black powder precursor, cooling to obtain a micro-brown powder, and grinding the micro-brown powder to obtain the lithium-rich cathode material. The lithium-rich cathode material of the lithium ion battery prepared by the method has the advantages of high energy density, good cycle and rate performance and the like, does not contain cobalt element with high toxicity and high cost, is simple and convenient in preparation method, is low in cost and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to a lithium-rich cathode material of a lithium ion battery and a preparation method thereof.
Background
Layered transition metal oxide LiMO2(M ═ Co, Ni …) is the most widely used positive electrode material for lithium secondary batteries, among which LiCoO2The anode material promotes the process of miniaturization of various electronic products in the last two decades, and creates great economic and social benefits. However, in the face of the rapidly growing new energy electric vehicle market, LiCoO2The performance of the material can not meet the capacity of the vehicle-mounted battery>200 mAh/g. Meanwhile, Co element has the problems of rare reserves, certain toxicity, high cost and the like, and researchers in various countries are forced to develop a layered structure cathode material with higher energy density, low cobalt and even no Co.
In response to this trend, several new layered cathode materials with low Co and even no Co, such as NCM, NCA, MNA, etc., have been developed in recent years. Lithium-rich manganese cathode material Li with high voltage and high energy density2MnO3Has attracted a great deal of attention. The theoretical energy density of the material can reach nearly 400mAh/g, the energy density far exceeds 200mAh/g required by a new energy electric automobile, and the material does not contain Co element and is considered as the next generation anode material with great potential. However, Li2MnO3The positive electrode material has the problems of poor conductivity, low cycle retention rate, serious voltage attenuation, low first coulombic efficiency and the like. To solve the above problems, 0.5Li was subsequently developed2MnO3·0.5LiNi0.5Mn0.5O2However, the performance of the positive electrode material still does not meet the requirements of commercial lithium batteries well, and although the cycle performance and conductivity of the positive electrode material are improved, the performance of the positive electrode material applied to commercial positive electrodes needs to be further improved.
Lithium manganese 0.5Li rich2MnO3·0.5LiNi0.5Mn0.5O2The high capacity of the material is mainly derived from C2/m phase, Li2MnO3In charging and dischargingIn the electrical process, lattice O participates in energy storage. However, part of O is also taken out of the lattice to form oxygen vacancy, and the pair is located in [ MnO6 ]]The stability of the octahedral central Mn atom is adversely affected, resulting in the participation of Mn ions in charge compensation from Mn during charging and discharging4+To Mn3+And reducing, and further generating a Mn compact layer phase by migration in the crystal lattice, so that the electrochemical performance of the lithium-rich manganese anode material is attenuated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a lithium-rich cathode material of a lithium ion battery and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:
one aspect of the present invention provides a method for preparing a lithium-rich cathode material for a lithium ion battery, comprising:
s1: dissolving a lithium source material, a nickel source material and a manganese source material in deionized water, and adjusting the pH value to be acidic to form a green transparent solution;
s2: adding a gallium source material into the green transparent solution until the gallium source material is completely dissolved, adding a proper amount of absolute ethyl alcohol and polyethylene glycol, and heating in a water bath to obtain a green gelatinous solid;
s3: burning and grinding the green gelatinous solid to obtain a black powder precursor;
s4: and calcining the black powder precursor, cooling to obtain a micro-brown powder, and grinding the micro-brown powder to obtain the lithium-rich cathode material.
In one embodiment of the present invention, the lithium source material is LiNO3(lithium nitrate), the nickel source material is Ni (CH)3COO)2·4H2O (nickel acetate), and the manganese source material is Mn (CH)3COO)2·4H2O (manganese acetate), the gallium source material is Ga (NO)3)3·xH2O (gallium nitrate).
In an embodiment of the present invention, the S1 includes:
s1.1: respectively weighing proper amount of LiNO according to the molar ratio of 1.2:0.32:0.48-a: a3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05；
S1.2: mixing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Sequentially adding a proper amount of deionized water, and adjusting the pH to 2-4;
s1.3: stirring at the room temperature at the rotating speed of 800-900 r/min for 2-3 h to obtain a green transparent solution.
In one embodiment of the present invention, the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH219-20 times of the total mass of O.
In an embodiment of the present invention, the S2 includes:
s2.1: adding weighed Ga (NO) into the green transparent solution3)3·xH2O and stirring for 20-40 min;
s2.2: adding ethanol with the same volume as the deionized water into the solution of S2.1, and stirring for 10-20 min;
s2.3: adding polyethylene glycol into the solution of S2.2 drop by drop, and stirring for at least 4 hours at a rotating speed of 300-400 r/min under a sealed condition to obtain a green colloidal solution;
s2.4: and heating the green colloidal solution in water bath at 70-100 ℃ for 5-7 h, stirring at the rotating speed of 350-450 r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
In one embodiment of the invention, the polyethylene glycol has a molecular weight of 400.
In one embodiment of the present invention, the molar ratio of the polyethylene glycol to the metal ions is 1.5:1, and the total number of moles of the metal ions is MM＝MLi+MNi+MMn+MGaWherein M isLiRepresents LiNO3Molar number of Li element in (M)NiRepresents Ni (CH)3COO)2·4H2Molar number of Ni element in O, MMnRepresents Mn (CH)3COO)2·4H2Molar number of Mn element in O, MGaRepresents Ga (NO)3)3·xH2Mole number of Ga element in O.
In an embodiment of the present invention, the S3 includes:
s3.1: pouring the green gelatinous solid into a crucible with a cover, putting the crucible into a muffle furnace, heating to 400-500 ℃ at a heating rate of 15-20 ℃/min, and carrying out heat preservation combustion for 2-4 h to obtain a loose block;
s3.2: and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
In an embodiment of the present invention, the S4 includes:
pouring the black powder precursor into a crucible with a cover, putting the crucible with the cover into a muffle furnace, heating to 500-600 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2-4 h; then heating to 890-950 ℃ at the speed of 2 ℃/min and preserving the heat for 20-25 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.48-aGaaO2A lithium-rich positive electrode material, wherein 0<a<0.05。
The invention also provides a lithium-rich cathode material of a lithium ion battery, which is prepared by the preparation method in any one of the embodiments.
Compared with the prior art, the invention has the beneficial effects that:
1. the lithium-rich cathode material of the lithium ion battery prepared by the method has the advantages of high energy density, good cycle and rate performance and the like; meanwhile, the material does not contain cobalt element with high toxicity and high cost, the preparation method is simple and convenient, the cost is low, and the material is environment-friendly.
2. Compared with a common coprecipitation method, a sol-gel method, a hydrothermal method and the like, the combustion method mainly obtains a target material by selecting a proper combustion improver and a proper dispersing agent and combining a specific preparation process, and the preparation method is a simple synthesis method of the lithium ion battery anode material, has low requirements on production conditions and has high production efficiency. The performance of the synthesized material is stable, and the prepared lithium-rich manganese anode material has low voltage attenuation and high cycle retention rate.
3. In the preparation method, the precursor is synthesized by adopting a combustion reaction method which is simple in preparation material and easy to reproduce, and then the lithium ion battery anode material Li with high specific capacity performance is prepared by controlling the calcination temperature and time1.2Ni0.32Mn0.46Ga0.02O2The discharge specific capacity under 0.05C multiplying power is up to 282.5mAh/g, the discharge specific capacity under 1C multiplying power can be up to 202mAh/g, the cycle retention rate is 90.5% after 200 cycles, the voltage attenuation is only 0.07V after 100 cycles, and the discharge specific capacity under 10C multiplying power can be up to 150 mAh/g.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
Fig. 1 is a flow chart of a method for preparing a lithium-rich cathode material of a lithium ion battery according to an embodiment of the present invention;
FIG. 2 is Li prepared at 0.05C according to an embodiment of the present invention1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A first-loop specific capacity-voltage curve diagram of the anode material;
FIG. 3 is a graph of Li prepared by example of the present invention cycled at 1C for 200 cycles1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A positive electrode material cycle number-specific capacity curve chart;
FIG. 4 is a graph of Li prepared by the example of the present invention cycled at 1C for 200 cycles1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A positive electrode material cycle number-median voltage curve chart;
FIG. 5 is at 0Li prepared by the embodiment of the invention for 5 cycles at 1C, 0.2C, 0.5C, 1C, 2C, 5C, 7C, 10C1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A cycle number-specific capacity curve diagram of the anode material.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on a lithium-rich cathode material of a lithium ion battery and a preparation method thereof according to the present invention with reference to the accompanying drawings and the detailed embodiments.
The foregoing and other technical matters, features and effects of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings. The technical means and effects of the present invention adopted to achieve the predetermined purpose can be more deeply and specifically understood through the description of the specific embodiments, however, the attached drawings are provided for reference and description only and are not used for limiting the technical scheme of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or device that comprises a list of elements does not include only those elements but may include other elements not expressly listed. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element.
Example one
Referring to fig. 1, fig. 1 is a flow chart of a method for preparing a lithium-rich cathode material of a lithium ion battery according to an embodiment of the present invention. The preparation method comprises the following steps:
s1: dissolving a lithium source material, a nickel source material and a manganese source material in deionized water, and adjusting the pH value to be acidic to form a green transparent solution.
The lithium source material is LiNO3The nickel source material is Ni (CH)3COO)2·4H2O, the manganese source material is Mn (CH)3COO)2·4H2O。
S1 of the present embodiment includes:
s1.1: respectively weighing proper amount of LiNO according to the molar ratio of 1.2:0.32:0.48-a: a3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05；
S1.2: mixing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Sequentially adding a proper amount of deionized water, and adjusting the pH to 2-4, wherein the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH219-20 times of the total mass of O.
In this step, hydrochloric acid (HCl) or oxalic acid (H) may be used for pH adjustment2C2O4) And the like.
S1.3: stirring at the room temperature at the rotating speed of 800-900 r/min for 2-3 h to obtain a green transparent solution.
S2: adding a gallium source material into the green transparent solution until the gallium source material is completely dissolved, adding a proper amount of absolute ethyl alcohol and polyethylene glycol, heating in a water bath to obtain a green gelatinous solid, wherein the gallium source material is Ga (NO)3)3·xH2O。
The S2 includes:
s2.1: ga (NO) weighed in step S1.1 is added to the green transparent solution3)3·xH2O and stirring for 20-40 min;
s2.2: adding ethanol with the same volume as the deionized water into the solution of S2.1, and stirring for 10-20 min;
s2.3: adding polyethylene glycol into the solution of S2.2 drop by drop, and stirring for at least 4 hours at a rotating speed of 300-400 r/min under a sealed condition to obtain a green colloidal solution; wherein the molecular weight of the polyethylene glycol is 400.
The molar ratio of the polyethylene glycol to the metal ions is 1.5:1, and the total molar number of the metal ions is MM＝MLi+MNi+MMn+MGaWherein M isLiRepresents LiNO3Molar number of Li element in (M)NiRepresents Ni (CH)3COO)2·4H2Molar number of Ni element in O, MMnRepresents Mn (CH)3COO)2·4H2Molar number of Mn element in O, MGaRepresents Ga (NO)3)3·xH2Mole number of Ga element in O.
S2.4: and heating the green colloidal solution in water bath at 70-100 ℃ for 5-7 h, stirring at the rotating speed of 350-450 r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
S3: and burning and grinding the green gelatinous solid to obtain a black powder precursor.
Specifically, the green gelatinous solid is poured into a crucible with a cover, the crucible is placed into a muffle furnace, the temperature is raised to 400-500 ℃ at the heating rate of 15-20 ℃/min, and the mixture is subjected to heat preservation and calcination for 2-4 hours to obtain a loose block; and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
S4: and calcining the black powder precursor, cooling to obtain a micro-brown powder, and grinding the micro-brown powder to obtain the lithium-rich cathode material.
Specifically, the black powder precursor is poured into a crucible with a cover, the crucible with the cover is placed into a muffle furnace, the temperature is raised to 500-600 ℃ at the speed of 2 ℃/min, and the temperature is kept for 2-4 h; then heating to 890-950 ℃ at the speed of 2 ℃/min and preserving the heat for 20-25 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.48-aGaaO2A lithium-rich positive electrode material, wherein 0<a<0.05。
In this example, Ga element was introduced as a stabilizer to stabilize the lattice O, thereby improving the stability of the material and suppressing the occurrence of lattice collapse, heterogeneous phase generation, and the like due to O deintercalation. Meanwhile, compared with Mn, Ni is not easy to migrate, and the generation of Mn compact layer phase can be inhibited by properly improving Ni, so that the cycle performance of the material is improved. And with the increase of the Ni content, the material voltage attenuation is also obviously inhibited. Therefore, the content of Ni in the lithium-rich manganese material can be properly increased, the transition metal element Ga is introduced, and a new solid solution material is formed by regulation and control.
Li prepared in this example1.2Mn0.48-aNi0.32GaaO2(0<a<0.05) a positive electrode material which is substantially a solid solution material having a structural formula of 0.5Li2MnO3·0.5LiNi0.8Mn0.2-aGaaO2(0<a<0.05). Wherein Li2MnO3Belongs to a C/2m space group and is a monoclinic layered structure, LiNi0.8Mn0.2-aGaaO2Belongs to R-3m space group and is alpha-NaFeO2A layered structure.
This example preparation of Li1.2Mn0.48-aNi0.32GaaO2(0<a<0.05) the method of the positive electrode material is a combustion method, compared with a common coprecipitation method, a sol-gel method, a hydrothermal method, and the like. The combustion method is a simple synthesis method of the lithium ion battery anode material, has low requirements on production conditions and high production efficiency, and mainly obtains the target material by selecting a proper combustion improver and a proper dispersing agent and combining a specific preparation process. The performance of the synthesized material is stable, and the prepared lithium-rich manganese positive electrode material 0.5Li2MnO3·0.5LiNi0.8Mn0.15Ga0.05O2Has lower voltage attenuation and higher cycle retention rate.
Example two
On the basis of the above embodiments, this embodiment provides another preparation method of a lithium-rich cathode material for a lithium ion battery, where the preparation method includes:
step 1: respectively weighing appropriate amount of the pure substances according to the molar ratio of 1.2:0.32:0.48-a: a>99% LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05, in this example, a is 0.01, i.e. the above molar ratio is 1.27:0.32:0.47: 0.01; weighing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Adding a proper amount of deionized water in sequence, and adjusting the pH value to 2 by using acid; stirring at room temperature at the rotating speed of 800r/min for 3h to obtain a green transparent solution.
In this embodiment, the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH 220 times of the total mass of O.
Step 2: gallium nitrate (Ga (NO) weighed in step 1 was added3)3·xH2O) and stirring for 30min to completely dissolve the ethanol, and stirring for 20min with the ethanol with the same volume as the deionized water; adding polyethylene glycol dropwise, and stirring for 4h at a rotating speed of 400r/min under a sealed condition to obtain a green colloidal solution, wherein the molecular weight of the polyethylene glycol is 400, and the molar ratio of the polyethylene glycol to metal ions is 1.5: 1; and then heating the green colloidal solution in a water bath at 70 ℃ for 7h, stirring at the rotating speed of 450r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
And step 3: pouring the green gelatinous solid into a crucible with a cover, putting the crucible into a muffle furnace, heating to 500 ℃ at a heating rate of 20 ℃/min, and carrying out heat preservation combustion for 2h to obtain a loose block; and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
When the green gel-like solid was poured into the crucible with the lid, the green gel-like solid could not exceed 1/4 of the crucible capacity.
And 4, step 4: pouring the black powder precursor into a crucible with a cover, putting the crucible with the cover into a muffle furnace, heating to 600 ℃ at the speed of 2 ℃/min, and preserving heat for 2 hours; then heating to 950 ℃ at the speed of 2 ℃/min and preserving heat for 20 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.47Ga0.01O2A lithium-rich cathode material.
EXAMPLE III
On the basis of the above embodiments, this embodiment provides another preparation method of a lithium-rich cathode material for a lithium ion battery, where the preparation method includes:
step 1: respectively weighing appropriate amount of the pure substances according to the molar ratio of 1.2:0.32:0.48-a: a>99% LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05, in this example, a is 0.02, i.e., the above molar ratio is 1.27:0.32:0.46: 0.02; weighing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Adding the mixture into a proper amount of deionized water in sequence, and adjusting the pH to 3 by using oxalic acid; stirring at the room temperature for about 2 hours at the rotating speed of 900r/min to obtain a green transparent solution.
In this embodiment, the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH219 times of the total mass of O.
Step 2: gallium nitrate (Ga (NO) weighed in step 1 was added3)3·xH2O) and stirring for 25min to completely dissolve the ethanol, and stirring for 15min with ethanol with the same volume as the deionized water; adding polyethylene glycol dropwise, stirring at 300r/min for 6h under sealed condition to obtain green colloidal solution with molecular weight of 400,the molar ratio of the polyethylene glycol to the metal ions is 1.5: 1; and then heating the green colloidal solution in a water bath at 100 ℃ for 5 hours, stirring at the rotating speed of 350r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
And step 3: pouring the green gelatinous solid into a crucible with a cover, putting the crucible into a muffle furnace, heating to 400 ℃ at a heating rate of 10 ℃/min, and carrying out heat preservation combustion for 4 hours to obtain a loose block; and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
When the green gel-like solid was poured into the crucible with the lid, the green gel-like solid could not exceed 1/4 of the crucible capacity.
And 4, step 4: pouring the black powder precursor into a crucible with a cover, putting the crucible with the cover into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 4 hours; then heating to 890 ℃ at the speed of 2 ℃/min and preserving heat for 25 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.46Ga0.02O2A lithium-rich cathode material.
Example four
On the basis of the above embodiments, this embodiment provides another preparation method of a lithium-rich cathode material for a lithium ion battery, where the preparation method includes:
step 1: respectively weighing appropriate amount of the pure substances according to the molar ratio of 1.2:0.32:0.48-a: a>99% LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05, in this example, a is 0.03, i.e., the above molar ratio is 1.27:0.32:0.45: 0.03; weighing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Adding a proper amount of deionized water in sequence, and adjusting the pH value to 4 by using acid; stirring at room temperature at 850r/min for about 3h to obtain green transparent solution.
In this embodiment, the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH219.5 times of the total mass of O.
Step 2: gallium nitrate (Ga (NO) weighed in step 1 was added3)3·xH2O) and stirring for 25min to completely dissolve the ethanol, and stirring for 15min with ethanol with the same volume as the deionized water; adding polyethylene glycol dropwise, and stirring for 5h at a rotating speed of 350r/min under a sealed condition to obtain a green colloidal solution, wherein the molecular weight of the polyethylene glycol is 400, and the molar ratio of the polyethylene glycol to metal ions is 1.5: 1; and then heating the green colloidal solution in a water bath at 80 ℃ for 6 hours, stirring at a rotating speed of 400r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
And step 3: pouring the green gelatinous solid into a crucible with a cover, putting the crucible into a muffle furnace, heating to 450 ℃ at a heating rate of 15 ℃/min, and carrying out heat preservation combustion for 3h to obtain a loose block; and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
When the green gel-like solid was poured into the crucible with the lid, the green gel-like solid could not exceed 1/4 of the crucible capacity.
And 4, step 4: pouring the black powder precursor into a crucible with a cover, putting the crucible with the cover into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, and preserving heat for 3 hours; then heating to 920 ℃ at the speed of 2 ℃/min and preserving heat for 21 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.45Ga0.03O2A lithium-rich cathode material.
The invention also provides a lithium-rich cathode material of a lithium ion battery, which is prepared by the preparation method in any one of the embodiments, and the lithium-rich cathode material of the lithium ion battery comprises the following components: li1.2Ni0.32Mn0.48-aGaaO2Wherein, 0<a<0.05。
The lithium-rich cathode material Li of the lithium ion battery prepared by the method of the embodiment of the invention is shown in the following by a comparative experiment1.2Ni0.32Mn0.46Ga0.02O2Further elucidating the properties of (a).
Referring to FIG. 2, FIG. 2 shows Li prepared at 0.05C according to an embodiment of the present invention1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2The first circle specific capacity-voltage curve diagram of the anode material. It can be seen that the lithium-rich cathode material Li prepared by the method of the embodiment of the invention1.2Ni0.32Mn0.46Ga0.02O2The discharge capacity at 0.05C is 282mAh/g, the first coulombic efficiency is 77.13 percent and Li1.2Ni0.2Mn0.6O2The performances of the primary coulombic efficiencies of 250-270 mAh/g are similar to each other, wherein the coulombic efficiencies of the primary coulombic efficiencies of the coulombic are 75%.
Referring to FIG. 3, FIG. 3 shows a cycle of 200 cycles of Li prepared according to an embodiment of the present invention at 1C1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A cycle number-specific capacity curve diagram of the anode material. As can be seen, Li1.2Ni0.32Mn0.46Ga0.02O2After the anode material is cycled for 200 circles under 1C, the initial discharge specific capacity is 202mAh/g, the discharge specific capacity is 183mAh/g after 200 circles, and the cycle retention rate is 90.59%. With Li1.2Ni0.2Mn0.6O2Compared with the cycle retention rate of only 75% after the positive electrode material is cycled for 200 circles at 1C, the Li1.2Ni0.32Mn0.46Ga0.02O2The cycle life of the material is obviously prolonged. And Li1.2Ni0.2Mn0.6O2The first circle of the positive electrode material 1C only has the discharge specific capacity of 175mAh/g, which is lower than that of Li1.2Ni0.32Mn0.46Ga0.02O2The specific discharge capacity of the positive electrode material is 202 mAh/g.
Referring to FIG. 4, FIG. 4 shows a cycle of 200 cycles of Li prepared according to an embodiment of the present invention at 1C1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2And (3) a positive electrode material cycle number-median voltage curve chart. It can be seen that after 200 cycles at 1C, Li1.2Ni0.32Mn0.46Ga0.02O2The voltage attenuation of the material is well inhibited, and the material is prepared from Li1.2Ni0.2Mn0.6O2The original 200 turns of the material are reduced from 0.29V to 0.13V, and the voltage retention ratio is increased from 80% to 96%.
Referring to FIG. 5, FIG. 5 shows Li prepared by embodiments of the present invention at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 7C, and 10C for 5 cycles1.2Ni0.32Mn0.46Ga0.02O2Cathode material and conventional Li1.2Ni0.2Mn0.6O2A cycle number-specific capacity curve diagram of the anode material. As can be seen, Li1.2Ni0.32Mn0.46Ga0.02O2Materials and Li1.2Ni0.2Mn0.6O2The material is cycled for 5 circles under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 7C and 10C respectively, Li1.2Ni0.32Mn0.46Ga0.02O2The material has better performance when being charged quickly. Li1.2Ni0.32Mn0.46Ga0.02O2The material still maintains the specific capacity of 150mAh/g under the high rate of 10C, which is the same as the LiCoO commonly used by commercial batteries2The specific capacity of the cathode material under the low rate of 1C is equivalent.
In conclusion, the lithium-rich cathode material of the lithium ion battery prepared by the method has the advantages of high energy density, good cycle and rate performance and the like; meanwhile, the material does not contain cobalt element with high toxicity and high cost, the preparation method is simple and convenient, the cost is low, and the material is environment-friendly; compared with a common coprecipitation method, a sol-gel method, a hydrothermal method and the like, the combustion method mainly obtains a target material by selecting a proper combustion improver and a proper dispersing agent and combining a specific preparation process, and the preparation method is a simple synthesis method of the lithium ion battery anode material, has low requirements on production conditions and has high production efficiency. The performance of the synthesized material is stable, and the prepared lithium-rich manganese anode material has low voltage attenuation and high cycle retention rate.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of a lithium-rich cathode material of a lithium ion battery is characterized by comprising the following steps:
s1: dissolving a lithium source material, a nickel source material and a manganese source material in deionized water, and adjusting the pH value to be acidic to form a green transparent solution;
s2: adding a gallium source material into the green transparent solution until the gallium source material is completely dissolved, adding a proper amount of absolute ethyl alcohol and polyethylene glycol, and heating in a water bath to obtain a green gelatinous solid;
s3: burning and grinding the green gelatinous solid to obtain a black powder precursor;
s4: and calcining the black powder precursor, cooling to obtain a brownish powder, and grinding and sieving the brownish powder to obtain the lithium-rich cathode material.
2. The method for preparing the lithium-rich cathode material of the lithium ion battery of claim 1, wherein the lithium source material is LiNO3The nickel source material is Ni (CH)3COO)2·4H2O, the manganese source material is Mn (CH)3COO)2·4H2O, the gallium source material is Ga (NO)3)3·xH2O。
3. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 2, wherein the step S1 comprises:
s1.1: respectively weighing proper amount of LiNO according to the molar ratio of 1.2:0.32:0.48-a: a3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH2O, wherein, 0<a<0.05；
S1.2: mixing Mn (CH)3COO)2·4H2O、Ni(CH3COO)2·4H2O and LiNO3Sequentially adding a proper amount of deionized water, and adjusting the pH to 2-4;
s1.3: stirring at the room temperature at the rotating speed of 800-900 r/min for 2-3 h to obtain a green transparent solution.
4. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 3, wherein the mass of the deionized water is LiNO3、Ni(CH3COO)2·4H2O、Mn(CH3COO)2·4H2O and Ga (NO)3)3·xH219-20 times of the total mass of O.
5. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 2, wherein the step S2 comprises:
s2.1: adding weighed Ga (NO) into the green transparent solution3)3·xH2O and stirring for 20-40 min;
s2.2: adding ethanol with the same volume as the deionized water into the solution of S2.1, and stirring for 10-20 min;
s2.3: adding polyethylene glycol into the solution of S2.2 drop by drop, and stirring for at least 4 hours at a rotating speed of 300-400 r/min under a sealed condition to obtain a green colloidal solution;
s2.4: and heating the green colloidal solution in water bath at 70-100 ℃ for 5-7 h, stirring at the rotating speed of 350-450 r/min to evaporate deionized water and ethanol, and standing to form a green gelatinous solid.
6. The method for preparing the lithium-rich cathode material of the lithium ion battery as claimed in claim 5, wherein the molecular weight of the polyethylene glycol is 400.
7. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 5, wherein the molar ratio of the polyethylene glycol to the metal ions is 1.5:1, and the total number of the metal ions is MM＝MLi+MNi+MMn+MGaWherein M isLiRepresents LiNO3Molar number of Li element in (M)NiRepresents Ni (CH)3COO)2·4H2Molar number of Ni element in O, MMnRepresents Mn (CH)3COO)2·4H2Molar number of Mn element in O, MGaRepresents Ga (NO)3)3·xH2Mole number of Ga element in O.
8. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 2, wherein the step S3 comprises:
s3.1: pouring the green gelatinous solid into a crucible with a cover, putting the crucible into a muffle furnace, heating to 400-500 ℃ at a heating rate of 15-20 ℃/min, and carrying out heat preservation combustion for 2-3 h to obtain a loose block;
s3.2: and grinding the loose block, and sieving the ground loose block by a 300-mesh sieve to obtain a uniform black powder precursor.
9. The method for preparing the lithium-rich cathode material of the lithium ion battery according to claim 2, wherein the step S4 comprises:
pouring the black powder precursor into a crucible with a cover, putting the crucible with the cover into a muffle furnace, heating to 500-600 ℃ at the speed of 2 ℃/min, and keeping the temperature for 2-4 h; then heating to 890-950 ℃ at the speed of 2 ℃/min and preserving the heat for 20-25 h; naturally cooling to room temperature, grinding, and sieving with 300 mesh sieve to obtain brown powder, i.e. target product Li1.2Ni0.32Mn0.48- aGaaO2A lithium-rich positive electrode material, wherein 0<a<0.05。
10. A lithium-rich cathode material for a lithium ion battery, which is prepared by the preparation method of any one of claims 1 to 9.
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