CN102646824A - Lithium ion battery anode material and preparation method thereof - Google Patents
Lithium ion battery anode material and preparation method thereof Download PDFInfo
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- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 239000011777 magnesium Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 7
- 239000001095 magnesium carbonate Substances 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 6
- 229940069446 magnesium acetate Drugs 0.000 claims description 6
- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 229910015645 LiMn Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005536 Jahn Teller effect Effects 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015155 LixMn2-x-yMy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- -1 compound carbonate Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery anode material Li1+xMn2-x-yMgyO4, which is prepared in the following method of: A, mixing lithium source compound, manganese source compound and magnesium source compound according to the chemical stoichiometric ratios that the ratio of Li to Mn is 0.54-0.6 and the ratio of Mg to the Mn is 0.015-0.03 and grinding; B, putting the compacted mixture into a high temperature resistor furnace, heating the mixture in oxidizing gas at the speed of 2-5 DEG C/min, after keeping the temperature at 650 DEG C for 6H, raising the temperature to 700-850 DEG C, keeping the temperature for 16-22h, and then slowly cooling the mixture in the oxidizing atmosphere to a room temperature along with the furnace; C, grinding sinter again, carrying out size grading, and sieving with a sieve of 400 meshes so as to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgy04; and preferably D, adding metal cations in the preparing process. The structure of the material is more stable, raw material resources are rich, the cost is lower, and the safety is high.
Description
Technical Field
The invention relates to a lithium ion battery anode material, and belongs to the field of preparation of new energy material lithium ion battery anode materials.
Background
Lithium ion secondary batteries have been widely put into practical use in recent years in large quantities because they have a high voltage, are excellent in charge and discharge characteristics, and are lightweight and small in size, and particularly, there is a strong demand for lithium ion secondary batteries having a high electromotive force of 4V. As such lithium ion secondary batteries, those using cobalt or a composite oxide of nickel and lithium as a positive electrode active material are known. However, cobalt and nickel are expensive, easily cause environmental pollution, and have the problem of possible resource exhaustion in the future.
Lithium manganate is a composite oxide of manganese and lithium and has the chemical formula LiMn2O4The compound has a spinel crystal structure and can be used as a positive electrode active material of a 4V-grade lithium ion secondary battery. In addition, because the raw material manganese is abundant and cheap, LiMn is a positive electrode material of increasingly developed power lithium ion batteries2O4The electrode material has attractive prospects. However, LiMn2O4Electrode materials suffer from a number of disadvantages, for example: the Jahn-Teller effect causes lattice distortion; HF generated after decomposition of the electrolyte tends to cause Mn3+Dissolving; the material is easy to be seriously attenuated at high temperature (above 55 ℃), and the like. For this reason, LiMn is generally replaced by a doped metal cation2O4Part of Mn ions in the structure generate spinel phase LixMn2-x-yMyO4(where M ═ Li, Mg, Cr, Ni, Cu, Fe, etc.) to improve the structural stability of the material, suppress the Jahn-Teller effect, enhance the cycle performance of the electrode material, and the like.
The anode material LiMn of the lithium ion battery at present2O4The synthesis method mainly comprises the following steps: solid phase method, molten salt method, sol-gel method, composite carbonate method, emulsion dry bath method, spray drying pyrolysis method, etc. Some methods can prepare LiMn with better electrochemical property2O4A positive electrode material, howeverThe preparation process is complex, the raw material cost is high, and the like, and the factors of commercialization and large-scale production exist. For example:
the material precursor prepared by the sol-gel method is uniformly mixed, the gel heat treatment temperature is low, and the final product particles are uniform, but the method has complex process and higher cost by adopting an organic solvent as a chelating agent, and is not suitable for industrial production.
LiMn prepared by molten salt method2O4The final product of the material is a spinel phase, the crystal structure is good, the electrochemical performance is good, but the cosolvent lithium chloride is washed away finally, so that the waste of raw materials is caused, the environment is polluted, and the mass industrial production is not facilitated.
The compound carbonate method has the disadvantages of raw material loss and long sample preparation time when anions are washed, and the required lithium stoichiometry cannot be exactly calculated in the process of lithium preparation, so that impurity phases are easily generated to influence the electrochemical performance of the material.
Disclosure of Invention
The invention aims to improve the electrochemical performance of the material, reduce the production cost and enable the material to be industrially produced as soon as possible by doping metal cations and optimizing the preparation process on the basis of overcoming the defects of the various methods.
According to a first object of the invention, the invention provides a lithium ion battery cathode material Li1+xMn2-x-yMgyO4The lithium source compound, the manganese source compound and the magnesium source compound are prepared by the following method:
A. mixing and grinding a lithium-containing source compound, a manganese-source compound and a magnesium-source compound according to the stoichiometric ratio of Li/Mn (0.54-0.6) and Mg/Mn (0.015-0.03);
B. compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating the compacted mixture in oxidizing gas at the speed of 2-5 ℃/min, keeping the temperature at 650 ℃ for 6H, heating the compacted mixture to 700-850 ℃, keeping the temperature for 16-22H, and then slowly cooling the compacted mixture to room temperature along with the furnace in an oxidizing atmosphere;
C. grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4。
Wherein the lithium source compound is selected from one of lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is more than or equal to 99.5 percent, and the excess amount of the lithium source is 2-10 percent.
Wherein the manganese source compound is selected from one of manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide.
Wherein the magnesium source compound is selected from one of magnesium hydroxide, magnesium acetate and magnesium carbonate.
Wherein, metal cations are also doped, wherein the metal cations are selected from any one or the mixture of La, Cs, Y, In, Ti and AI.
After the scheme is adopted, the prepared lithium ion battery cathode material has the advantages of more stable structure, abundant raw material resources, lower cost, high safety, environmental friendliness, good cycle performance at high temperature (above 55 ℃), small capacity attenuation and the like, and can become the most promising and attractive cathode material in the development of future lithium ion batteries.
According to a second object of the present invention, the present invention provides a method for preparing a positive electrode material of a lithium ion battery, comprising: A. mixing and grinding a lithium-containing source compound, a manganese-source compound and a magnesium-source compound according to the stoichiometric ratio of Li/Mn (0.54-0.6) and Mg/Mn (0.015-0.03);
B. compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating the compacted mixture in oxidizing gas at the speed of 2-5 ℃/min, keeping the temperature at 650 ℃ for 6H, heating the compacted mixture to 700-850 ℃, keeping the temperature for 16-22H, and then slowly cooling the compacted mixture to room temperature along with the furnace in an oxidizing atmosphere;
C. the sinter is processed againGrinding and grading the particle size, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4。
Wherein, still include: D. the metal cations are simultaneously incorporated during the preparation process.
Wherein the lithium source compound is selected from one of lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is more than or equal to 99.5 percent, and the excess amount of the lithium source is 2-10 percent; or,
the manganese source compound is selected from one of manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide; or,
the magnesium source compound is selected from one of magnesium hydroxide, magnesium acetate and magnesium carbonate.
Wherein the oxidizing gas is air, oxygen or ozone.
Wherein, the metal cation is selected from any one of La, Cs, Y, In, Ti and AI or the mixture thereof.
After the scheme is adopted, the invention has the advantages that:
the cost of raw materials is low:
secondly, the preparation process is simple, easy to control, low in sintering temperature and the like, can reduce energy consumption, and is suitable for industrial production.
Drawings
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments so that the above advantages of the present invention will be more apparent.
FIG. 1A specific embodiment Li of the present invention1.06Mn1.92Mg0.02O4XRD spectrogram;
FIG. 2 exemplary embodiment of the invention Li1.06Mn1.92Mg0.02O4SEM spectrogram;
FIG. 3 shows an embodiment Li of the present invention1.06Mn1.92Mg0.02O4A charge-discharge curve diagram, wherein: the charge-discharge multiplying power is 1C, and the charge-discharge voltage range is 3.3-4.5V;
FIG. 4 exemplary embodiment of the present invention Li1.06Mn1.92Mg0.02O4Cyclic voltammetry curves;
FIG. 5 shows the cycle performance of the embodiment Li1.06Mn1.92Mg0.02O4 of the present invention, wherein: and the charge and discharge multiplying power is respectively 0.5C and 1C, and the cycle performance curve chart of the 20 th cycle.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The first product embodiment is as follows:
the applicant has conducted extensive studies and studies on LiMn2O4Proper amount of magnesium and lithium metal ions are doped in production raw materials, and the lithium ion battery anode material Li is prepared by production through the process researched by the invention1+xMn2-x-yMgyO4Has the characteristics of uniform particles, complete crystallization, stable electrochemical performance and the like. Due to Li1+xMn2-x-yMgyO4The positive electrode material has the advantages of more stable structure, abundant raw material resources, lower cost, high safety, environmental friendliness, good cycle performance at high temperature (above 55 ℃), small capacity attenuation and the like, and can become the most promising and attractive positive electrode material in the development of the future lithium ion battery.
To this end, based on the above findings, the applicant provides a positive electrode material Li for lithium ion batteries1+xMn2-x-yMgyO4The method comprises the following steps: lithium source compound, manganese source compound and magnesium source compound, and the method for preparing the sameThe compound is doped with metal cations and is prepared from a lithium source compound, a manganese source compound and a magnesium source compound by the following method:
A. mixing and grinding a lithium-containing source compound, a manganese-source compound and a magnesium-source compound according to the stoichiometric ratio of Li/Mn (0.54-0.6) and Mg/Mn (0.015-0.03);
B. compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating the compacted mixture in oxidizing gas at the speed of 2-5 ℃/min, keeping the temperature at 650 ℃ for 6H, heating the compacted mixture to 700-850 ℃, keeping the temperature for 16-22H, and then slowly cooling the compacted mixture to room temperature along with the furnace in an oxidizing atmosphere;
C. grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4。
Wherein the lithium source compound is selected from one of lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is more than or equal to 99.5 percent, and the excess amount of the lithium source is 2-10 percent.
Wherein the manganese source compound is selected from one of manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide.
Wherein the magnesium source compound is selected from one of magnesium hydroxide, magnesium acetate and magnesium carbonate.
Wherein, metal cations are doped simultaneously In the preparation process, and the metal cations are selected from any one of La, Cs, Y, In, Ti and AI or the mixture thereof.
After the scheme is adopted, the prepared lithium ion battery cathode material has the advantages of more stable structure, abundant raw material resources, lower cost, high safety, environmental friendliness, good cycle performance at high temperature (above 55 ℃), small capacity attenuation and the like, and can become the most promising and attractive cathode material in the development of future lithium ion batteries.
The first embodiment of the method comprises the following steps:
the invention provides a method for producing a lithium ion battery anode material Li1+xMn2-x-yMgyO4The method of (1), comprising the steps of:
(1) a step of mixing and grinding a lithium-containing source compound, a manganese-source compound, and a magnesium-source compound (containing crystal water) in a stoichiometric ratio;
(2) compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating and raising the temperature at the speed of 2-5 ℃/min in an oxidizing gas atmosphere, keeping the temperature at 650 ℃ for 6h, raising the temperature to 700-850 ℃, keeping the temperature for 16-22h, and then slowly cooling the mixture to room temperature along with the furnace in the oxidizing atmosphere;
(3) grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4And (4) performance.
Wherein the lithium source compound is selected from one of lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is more than or equal to 99.5 percent, and the excess amount of the lithium source is 2-10 percent; or,
the manganese source compound is selected from one of manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide; or,
the magnesium source compound is selected from one of magnesium hydroxide, magnesium acetate and magnesium carbonate.
Wherein the oxidizing gas is air, oxygen or ozone.
Wherein, metal cations are doped simultaneously In the preparation process, and the metal cations are selected from any one of La, Cs, Y, In, Ti and AI or the mixture thereof.
The invention has the advantages that:
the cost of raw materials is low:
secondly, the preparation process is simple, easy to control, low in sintering temperature and the like, can reduce energy consumption, and is suitable for industrial production;
the material prepared by the method has stable structure, can effectively inhibit Jahn-Teller effect and has high crystallinity; the electrochemical performance is stable, and the high-rate discharge performance is excellent; the charge and discharge rate was 1C, and after 50 cycles, the capacity fade was only 1.6% of the initial capacity, while the capacity remained essentially stable after 50 cycles of 0.5C charge and discharge.
The second method embodiment:
synthesizing lithium ion battery anode material Li by using battery-grade lithium carbonate, graded electrolytic manganese dioxide and electronic-grade light magnesium carbonate as raw materials1.06Mn1.92Mg0.02O4The method comprises the following steps:
1. according to the chemical formula Li of the target product1.06Mn1.92Mg0.02O4Calculating the consumption of various raw materials. Synthesis of 1 mol I Li1.06Mn1.92Mg0.02O40.53mol of Li are required2CO3，0.02mol MgCO3.2H2O，1.92mol MnO2. Taking into account Li2CO3The loss on ignition is increased by 6% of Li2CO3Thus Li2CO3Is 0.56 mol.
2. 0.56mol of Li2CO3、1.92mol MnO2、0.02mol MgCO3.2H2O is accurately weighed and mixed, and then is put into an agate lapping body to be ground for about 30 minutes
3. Compacting the mixture, putting the compacted mixture into a high-temperature resistance furnace, and heating the compacted mixture in oxidizing gas at a speed of 2-5 ℃/min to raise the temperature.
4. Heating to 650 ℃ and preserving the temperature for 6H. Continuously heating to 700-850 ℃ and preserving the temperature for 16-22h, and then slowly cooling to room temperature along with the furnace in an oxidizing atmosphere.
5. Grinding the sintered material again, grading the particle size, and sieving with a 400-mesh sieve to obtain the final product, namely the lithium ion battery anode material Li1.06Mn1.92Mg0.02O4。
Wherein, metal cations are doped simultaneously In the preparation process, and the metal cations are selected from any one of La, Cs, Y, In, Ti and AI or the mixture thereof.
The third method embodiment:
lithium ion battery anode material Li is synthesized by taking battery-grade lithium carbonate, graded electrolytic manganese dioxide, electronic-grade light magnesium carbonate and lanthanum trioxide as raw materials1.06Mn1.92Mg0.015La0.005O, comprising the following steps:
1. according to the chemical formula Li of the target product1.06Mn1.92Mg0.015La0.005O4Calculating the consumption of various raw materials.
Synthesis of Li1.06Mn1.92Mg0.015La0.005O40.52mol of Li are required2CO3，0.02molMgCO3·2H2O，1.92mol MnO2，0.0025molLa2O3In view of Li2CO3The loss on ignition is increased by 6% of Li2CO3Thus Li2CO3Is 0.56 mol.
2. 0.56mol of Li2CO3、1.92mol MnO2、0.02mol MgCO3·2H2O，0.0025molLa2O3Accurately weighed and mixed, and then put into an agate lapping body to be ground for about 30 minutes.
3. And compacting the mixture and then putting the compacted mixture into a high-temperature resistance furnace. Heating at a rate of 2-5 deg.C/min in an oxidizing gas atmosphere.
4. After the temperature is raised to 650 ℃ and the heat is preserved for 6H, the temperature is continuously raised to 700-850 ℃ and the heat is preserved for 16-22H, and then the furnace is slowly cooled to the room temperature in the oxidizing atmosphere.
5. Grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the final product of the lithium ion battery anodeMaterial Li1.06Mn1.92Mg0.015La0.005O4。
Wherein, metal cations are doped simultaneously In the preparation process, and the metal cations are selected from any one of La, Cs, Y, In, Ti and AI or the mixture thereof.
The advantages of the present invention are described in more detail below in conjunction with the test chart of the present invention.
FIG. 1 is an XRD spectrum of an embodiment Li1.06Mn1.92Mg0.02O4XRD spectrum in the invention;
it can be seen from XRD test that Li is prepared1.06Mn1.92Mg0.02O4The material is spinel structure, belonging to cubic system and Fd3m space group. The sample has no impure phase production, sharp and clear peak shape and higher strength, which indicates that the product has good crystallinity.
FIG. 2 shows an embodiment of the present invention, Li1.06Mn1.92Mg0.02O4SEM spectra of (a);
as can be seen from SEM, the sample has a typical spinel appearance, and is consistent with XRD test results, the sample is micron-sized particles, the crystal is regular, and the average grain size (D50) is about 16-18 μm.
FIG. 3 shows an embodiment of the present invention, Li1.06Mn1.92Mg0.02O4A charge-discharge curve diagram, wherein: the charge-discharge multiplying power is 1C, and the charge-discharge voltage range is 3.3-4.5V;
FIG. 4 exemplary embodiment of the present invention Li1.06Mn1.92Mg0.02O4Cyclic voltammetry curves;
FIG. 5 shows the cycle performance of the embodiment Li1.06Mn1.92Mg0.02O4 of the present invention, wherein: a cycle performance curve diagram of the 20 th cycle with the charge and discharge multiplying power of 0.5C and 1C respectively;
it can be seen from the figure that it has a very good performance curve.
It should be noted that the above-mentioned embodiments are only exemplary, and those skilled in the art can make various modifications and variations on the above-mentioned embodiments without departing from the scope of the invention.
It will be appreciated by persons skilled in the art that the foregoing detailed description is provided for the purpose of illustrating the invention and is not to be construed as limiting the invention. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. Lithium ion battery anode material Li1+xMn2-x-yMgyO4The lithium source compound, the manganese source compound and the magnesium source compound are prepared by the following method:
A. mixing and grinding a lithium-containing source compound, a manganese-source compound and a magnesium-source compound according to the stoichiometric ratio of Li/Mn (0.54-0.6) and Mg/Mn (0.015-0.03);
B. compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating the compacted mixture in oxidizing gas at the speed of 2-5 ℃/min, keeping the temperature at 650 ℃ for 6H, heating the compacted mixture to 700-850 ℃, keeping the temperature for 16-22H, and then slowly cooling the compacted mixture to room temperature along with the furnace in an oxidizing atmosphere;
C. grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4。
2. The lithium ion battery cathode material according to claim 1, wherein the lithium source compound is one selected from lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is greater than or equal to 99.5%, and the lithium source is in excess of 2-10%.
3. The positive electrode material for a lithium ion battery according to claim 1, wherein the manganese source compound is one selected from manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide.
4. The positive electrode material for a lithium ion battery according to claim 1, wherein the magnesium source compound is one selected from the group consisting of magnesium hydroxide, magnesium acetate, and magnesium carbonate.
5. The lithium ion battery positive electrode material according to claim 1, further comprising: and (3) doped metal cations, wherein the metal cations are selected from any one or a mixture of La, Cs, Y, In, Ti and AI.
6. Lithium ion battery anode material Li1+xMn2-x-yMgyO4The preparation method comprises the following steps:
A. mixing and grinding a lithium-containing source compound, a manganese-source compound and a magnesium-source compound according to the stoichiometric ratio of Li/Mn (0.54-0.6) and Mg/Mn (0.015-0.03);
B. compacting the mixture, then placing the compacted mixture into a high-temperature resistance furnace, heating the compacted mixture in oxidizing gas at the speed of 2-5 ℃/min, keeping the temperature at 650 ℃ for 6H, heating the compacted mixture to 700-850 ℃, keeping the temperature for 16-22H, and then slowly cooling the compacted mixture to room temperature along with the furnace in an oxidizing atmosphere;
C. grinding the sinter again, grading the granularity, and sieving with a 400-mesh sieve to obtain the target lithium ion battery anode material Li1+xMn2-x-yMgyO4。
7. The method for preparing the positive electrode material of the lithium ion battery according to claim 6, further comprising a step D: the metal cations are simultaneously incorporated during the preparation process.
8. The preparation method of the positive electrode material of the lithium ion battery according to claim 6, wherein the lithium source compound is one selected from lithium hydroxide, lithium acetate and lithium carbonate, the purity of the lithium source compound is more than or equal to 99.5%, and the lithium source is in excess of 2-10%; or,
the manganese source compound is selected from one of manganese hydroxide, manganese acetate, electrolytic manganese dioxide and chemical manganese dioxide; or,
the magnesium source compound is selected from one of magnesium hydroxide, magnesium acetate and magnesium carbonate.
9. The method for preparing a positive electrode material for a lithium ion battery according to claim 6, wherein the oxidizing gas is air, oxygen, or ozone.
10. The method for preparing the positive electrode material of the lithium ion battery according to claim 6, wherein the metal cation is selected from any one of La, Cs, Y, In, Ti and AI or a mixture thereof.
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