CN111082044A - Yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery - Google Patents
Yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 94
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 74
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000000463 material Substances 0.000 claims description 36
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- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 11
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- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
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- 239000011656 manganese carbonate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
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- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910016489 Mn1/2Ni1/2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- H01M4/52—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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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an yttrium-doped lithium-rich manganese-based lithium ion battery anode material, a preparation method thereof and a lithium ion battery1.2Ni0.2Mn0.6‑xYxO2Wherein x is more than 0 and less than or equal to 0.04; adding a lithium source, a nickel source, a manganese source and an yttrium source into an alcohol solvent, dissolving and mixing to obtain a metal salt solution, and drying the metal salt solution to obtain an intermediate; heating and sintering the intermediate to obtain a sintered product; and cooling to obtain the yttrium-doped lithium-rich manganese-based positive electrode material. The invention adopts a high-temperature solid phase method for preparation, has simple and convenient process, easily controlled reaction parameters, no agglomeration of powder particles, good filling property and large yield; the prepared structure is stable and stableThe ring performance is good, the multiplying power performance is excellent, and the capacity and voltage attenuation in the circulating process can be effectively inhibited.
Description
Technical Field
The invention relates to a lithium battery anode material, a preparation method and a lithium battery, in particular to an yttrium-doped lithium-rich manganese-based lithium ion battery anode material, a preparation method and a lithium ion battery.
Background
In recent years, lithium ion batteries are more and more widely applied to the market, and the characteristics of high capacity, light volume and the like enable the lithium ion batteries to be widely applied to the fields of electric vehicles, portable mobile phone equipment and the like. With the development of society, the application requirements are higher and higher, so that lithium ion batteries with excellent performance are needed to meet the social needs. One of the key factors determining the performance of a lithium ion battery is the selection and modification of the positive electrode material. The lithium-rich cathode material is widely concerned due to the advantages of high capacity, high working voltage, low cost and the like of the lithium-rich cathode material in the lithium ion battery, and if the defects of the lithium-rich cathode material can be overcome and the lithium-rich cathode material is successfully popularized and commercialized, the lithium-rich cathode material is greatly helpful for the global energy and environmental strategies.
Most of the researched and optimized lithium-rich manganese-based anode materials contain three elements including nickel, manganese and cobalt, and the lithium-rich manganese-based anode material is 0.5LiMO2·0.5Li2MnO3(M＝Mn1/2Ni1/2) Compared with other anode materials, the material selects and abandons expensive and toxic Co element, has higher charge and discharge capacity and lower price, has discharge specific capacity reaching 278mAh/g, and is an anode material with very wide application prospect in the lithium-rich battery market. But also has the disadvantages of poor cycle performance, fast capacity and voltage decay and poor rate performance. The conventional method for improving the electrochemical performance mainly comprises doping and cladding, for example, CN107644992A adopts a method of sodium ion doping to replace lithium ions, so as to improve the electrochemical performance of the lithium-rich manganese-based positive electrode material; CN 105895903A adopts anion fluorine chlorine bromine to dope and modify the material, and optimizes the electrochemical performance of the battery to a certain extent.
More than a few transition metal ions are used for doping, but various parameters of different doping elements have different influences on the doping effect. Generally, transition metal ions are used for replacing manganese ions of a transition metal layer in a lithium-rich manganese-based layered structure, such as co-precipitation method titanium doping of CN 107732229A, sol-gel method molybdenum doping of CN 107768664A, polymer template method niobium doping of CN109244444A and the like, and obvious improvement effects are obtained. In order to make metal ions easily doped into crystal lattices, elements with the radius equivalent to that of manganese ions are generally selected and used, and the radius is about 60 pm.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide an yttrium-doped lithium-rich manganese-based lithium ion battery anode material which has stable structure, good cycle performance and better rate performance and can effectively inhibit the capacity and voltage attenuation in the cycle process; the invention also aims to provide a preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery anode material, which adopts a high-temperature solid phase method for preparation, has simple and convenient process, easily controlled reaction parameters, no agglomeration of powder particles, good filling property and large yield; the invention also aims to provide a lithium ion battery.
The technical scheme is as follows: the yttrium-doped lithium-rich manganese-based lithium ion battery anode material is a layered material and has a chemical general formula of Li1.2Ni0.2Mn0.6-xYxO2Wherein x is more than 0 and less than or equal to 0.04.
Preferably, in the chemical formula, x is more than or equal to 0.02 and less than or equal to 0.04.
The invention also provides a preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery anode material, which adopts a high-temperature solid phase method and comprises the following steps:
(1) adding raw materials of a lithium source, a nickel source, a manganese source and an yttrium source into an alcohol solvent, dissolving and mixing to obtain a metal salt solution, and heating and drying the metal salt solution to obtain an intermediate;
mixing the metal salt compounds at stoichiometric ratio, adding alcohol solvent (such as ethanol) in water bath, heating, stirring to dissolve, mixing completely, and drying; considering that the lithium source is subjected to high-temperature calcination in the preparation process to generate loss, the lithium source can be slightly excessive, and the addition amount of the lithium source is 2-7% more than the theoretical value of the lithium source; the drying procedure can adopt conventional drying, microwave drying and vacuum drying;
(2) heating and sintering the intermediate to obtain a sintered product; and in order to ensure uniform heating and an atmosphere environment, the intermediate is put into a tubular furnace for heating and sintering.
(3) And cooling the sintered product to obtain the yttrium-doped lithium-rich manganese-based positive electrode material. The cooling mode can adopt natural cooling in a furnace, natural cooling in air or liquid nitrogen cooling, and the cooling rates of different cooling modes are different.
Preferably, the obtained intermediate is subjected to heating sintering, and the heating sintering process comprises low-temperature presintering and high-temperature heating, wherein the low-temperature presintering temperature is 350-550 ℃, and the low-temperature presintering time is 1-2 hours; the high-temperature heating temperature is 800-950 ℃, and the high-temperature heating time is 11-15 hours.
Preferably, in order to optimize the electrical performance of the anode material, the temperature rise rate needs to be controlled to be 1-10 ℃/min, and the temperature rise rate is not too fast or too slow; raising the temperature from room temperature to 350-550 ℃ at the speed of 1-10 ℃/min for low-temperature presintering, and then raising the temperature to 800-950 ℃ at the speed of 1-10 ℃/min for high-temperature heating.
The lithium source is at least one of lithium acetate dihydrate, lithium nitrate or lithium carbonate; the nickel source is at least one of nickel nitrate hexahydrate, nickel acetate or nickel carbonate; the manganese source is at least one of tetrahydrate manganese acetate, manganese nitrate or manganese carbonate; the yttrium source is at least one of yttrium nitrate hexahydrate or yttrium acetate.
Preferably, the alcoholic solvent is at least one of ethanol, propanol or isopropanol.
In order to further optimize the performance of the cathode material, the cooling is performed by using liquid nitrogen.
The invention also provides a lithium ion battery which comprises a positive electrode, wherein the positive electrode comprises the yttrium-doped lithium-rich manganese-based positive electrode material.
The invention principle is as follows: although the electrochemical performance can be improved by doping with transition metal ions, the doping metal ions in the prior art are about 60pm, and the invention replaces manganese ions in the layered lithium-rich manganese-based material with yttrium ions with the ionic radius of 90 pm. However, because the ion radius of the doping element is large, a plurality of problems in synthesis exist, and the difficulty in preparing the stable and agglomeration-free cathode material is large.
The invention adopts a high-temperature solid phase method, the solid interfaces are subjected to contact reaction, the generated powder particles do not have agglomeration phenomenon, the filling property is good, and the preparation process is simple, rapid and easy to control; and using metal ions with larger radius to produce other optimization effects on the structure under the condition of successful doping, such as yttrium ions with the ionic radius of 90 pm.
According to the invention, the manganese ions in the layered lithium-rich manganese-based material are replaced by the yttrium metal cation, and in the layered structure, the layer spacing is increased after the yttrium ions replace the manganese ions, so that the lithium ion extraction rate is increased, and the multiplying power problem of the lithium-rich manganese-based anode material is improved. In addition, ions with larger radius can play a pinning role on the laminated structure, and the problem of structural transformation of the material in the circulating process is inhibited, so that the circulating performance is improved, and the service life of the material is prolonged. Therefore, the invention replaces manganese ions in the layered lithium-rich manganese-based material with metal cation yttrium, thereby stabilizing the layered structure, improving the cycle performance of the material, increasing the interlayer spacing and improving the rate capability of the material. The yttrium-doped lithium-rich manganese-based positive electrode material can solve the problems of capacity attenuation and voltage attenuation in the material circulation process.
Has the advantages that: compared with the prior art, the method has the advantages that,
(1) according to the invention, manganese ions in the layered lithium-rich manganese-based material are replaced by yttrium, so that the layered structure is stabilized, the interlayer spacing is increased, and the purposes of inhibiting voltage and capacity attenuation and improving rate performance in the charge and discharge processes of the material are achieved; the yttrium-doped lithium-rich manganese-based positive electrode material provided by the invention has the advantages of stable structure, good cycle performance and excellent rate performance, and can effectively inhibit the capacity and voltage attenuation in the cycle process;
(2) according to the invention, manganese ions in the layered lithium-rich manganese-based material are replaced by adopting transition metal yttrium ions, and a high-temperature solid phase method is combined, so that the prepared layered lithium-rich manganese-based positive electrode material has the advantages of stable structure, no particle agglomeration, good filling property and great optimization effect on the electrochemical performance of the material;
(3) the method has the advantages of simple and convenient process steps, easily controlled reaction parameters, high yield and suitability for popularization and application.
Drawings
FIG. 1 is an SEM image of a sample of example 1;
FIG. 2 is an XRD spectrum of the sample of examples 1-5 at a diffraction angle in the range of 10-80 °;
FIG. 3 is a graph showing the cycle performance at 0.1C current for the samples of examples 1-5;
FIG. 4 is a graph comparing the rate capability of example 1, example 2 and example 10;
fig. 5 is a comparison of the capacity cycling decay of the cells of example 1 and example 10.
Detailed Description
The present invention will be described in further detail with reference to examples.
The reagents and starting materials used in the following examples are all commercially available.
Example 1:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2。
12.852g (0.126mol) of lithium acetate dihydrate, 13.965g (0.057mol) of manganese acetate tetrahydrate, 5.816g (0.020mol) of nickel nitrate hexahydrate and 1.149g (0.003mol) of yttrium nitrate hexahydrate are weighed, mixed, added with 50mL of ethanol solution, put into a water bath for heating and continuously stirring until fully dissolved and mixed, put the liquid into a drying box for evaporation drying, put the dried material into a tubular furnace, heat up to 450 ℃ at the speed of 5 ℃/min for low-temperature presintering for 1 hour, heat up to 900 ℃ at the speed of 5 ℃/min for continuous calcining for 12 hours, and take out from the furnace for rapid cooling (the cooling speed is about 20 ℃/min) to obtain the yttrium-doped lithium-rich manganese-based positive electrode material. The sample particles prepared by the reaction are polyhedral, and the average particle size is about 200 nm. An SEM image of the sample is shown in fig. 1.
The sample prepared by the embodiment is a typical polyhedral structure of the lithium-rich manganese-based material, and the size of the sample is about 200 nm; the characteristic peak of the XRD pattern of the sample is obvious and does not contain a foreign peak, which shows that the layered structure is clear and does not contain impurities.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps: mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 1, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Example 2:
this example prepares a lithium-rich manganese-based cathode material Li that is not doped with yttrium1.2Ni0.2Mn0.6O2。
The preparation process and procedure of this example were substantially the same as in example 1 except that yttrium nitrate was not added.
Mixing 0.126mol of lithium acetate dihydrate, 0.060mol of manganese acetate tetrahydrate and 0.020mol of nickel nitrate hexahydrate, adding 50mL of ethanol solution, heating in a water bath, continuously stirring until the mixture is fully dissolved and mixed, putting the liquid into a drying oven for evaporation drying, putting the dried material into a tubular furnace, heating from room temperature to 450 ℃ at the speed of 5 ℃/min for low-temperature pre-sintering for 1 hour, then heating to 900 ℃ at the speed of 5 ℃/min for continuous calcination for 12 hours, taking out from the furnace, and rapidly cooling (the cooling speed is about 20 ℃/min) to obtain the lithium-rich manganese-based positive electrode material which is not doped with yttrium.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps: mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 2, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Example 3:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.59Y0.01O2。
The preparation method and procedure of this example were substantially the same as in example 1 except that 0.001mol of yttrium nitrate hexahydrate and 0.059mol of manganese acetate tetrahydrate were added.
Mixing 0.126mol of lithium acetate dihydrate, 0.059mol of manganese acetate tetrahydrate, 0.001mol of yttrium nitrate hexahydrate and 0.020mol of nickel nitrate hexahydrate, adding 50mL of ethanol solution, heating in a water bath, continuously stirring until the mixture is fully dissolved and mixed, putting the liquid into a drying oven for evaporation drying, putting the dried material into a tubular furnace, heating from room temperature to 450 ℃ at the rate of 5 ℃/min, presintering for 1 hour at low temperature, then heating to 900 ℃ at the rate of 5 ℃/min, continuously calcining for 12 hours, taking out from the furnace, and rapidly cooling to obtain the yttrium-doped lithium-rich manganese-based positive electrode material.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps:
mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 3, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Example 4:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.58Y0.02O2。
The preparation method and procedure of this example were substantially the same as in example 1 except that 0.002mol of yttrium nitrate hexahydrate and 0.058mol of manganese acetate tetrahydrate were added.
Mixing 0.126mol of lithium acetate dihydrate, 0.058mol of manganese acetate tetrahydrate, 0.002mol of yttrium nitrate hexahydrate and 0.020mol of nickel nitrate hexahydrate, adding 50mL of ethanol solution, heating in a water bath, continuously stirring until the mixture is fully dissolved and mixed, putting the liquid into a drying oven for evaporation drying, putting the dried material into a tubular furnace, heating from room temperature to 450 ℃ at the rate of 5 ℃/min for presintering for 1 hour at a low temperature, then heating to 900 ℃ at the rate of 5 ℃/min for continuous calcination for 12 hours, taking out from the furnace, and rapidly cooling to obtain the yttrium-doped lithium-rich manganese-based positive electrode material.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps:
mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 4, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Example 5:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.56Y0.04O2。
The preparation method and procedure of this example were substantially the same as in example 1 except that 0.004mol of yttrium nitrate hexahydrate and 0.056mol of manganese acetate tetrahydrate were added.
Mixing 0.126mol of lithium acetate dihydrate, 0.056mol of manganese acetate tetrahydrate, 0.004mol of yttrium nitrate hexahydrate and 0.020mol of nickel nitrate hexahydrate, adding 50mL of ethanol solution, heating in a water bath, continuously stirring until the mixture is fully dissolved and mixed, putting the liquid into a drying oven for evaporation drying, putting the dried material into a tubular furnace, heating from room temperature to 450 ℃ at the rate of 5 ℃/min for presintering for 1 hour at a low temperature, then heating to 900 ℃ at the rate of 5 ℃/min for continuous calcination for 12 hours, taking out from the furnace, and rapidly cooling to obtain the yttrium-doped lithium-rich manganese-based positive electrode material.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps:
mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 5, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Example 6:
this example preparation of Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of the embodiment are basically the same as those of the embodiment 1, except that the sintering temperature is changed from 900 ℃ to 850 ℃ for 12 hours to synthesize the lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2And assembled into a battery.
Example 7:
this example preparation of Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of the embodiment are basically the same as those of the embodiment 1, except that the lithium-rich manganese-based cathode material Li is synthesized by only changing the high-temperature sintering temperature from 900 ℃ to 950 ℃ for 12 hours1.2Ni0.2Mn0.57Y0.03O2And assembled into a battery.
Comparing the data of examples 1, 6, 7 in table 1, the effect of sintering temperature on cycle performance and rate performance can be seen. It can be seen that the material properties also differ at different sintering temperatures. As can be seen, higher sintering temperatures can improve the cycling performance of the material, but can degrade the rate performance, balancing the two drawbacks when the temperature is 900 ℃.
Comparison of data items in Table 1 and examples 1, 6 and 7
Example 8:
according to the method of the embodiment 1, the cooling rate after sintering is changed, the lithium-rich manganese-based cathode material Li is synthesized by using the natural cooling in the tube furnace, wherein the cooling rate is about 5 ℃/min1.2Ni0.2Mn0.57Y0.03O2And assembled into a battery.
Example 9:
according to the method of the embodiment 1, the cooling rate after sintering is changed, liquid nitrogen is used for cooling, the cooling rate is about 100 ℃/min, and the lithium-rich manganese-based cathode material Li is synthesized1.2Ni0.2Mn0.57Y0.03O2And assembled into a battery.
The data of examples 1, 8 and 9 are shown in Table 2. It can be seen that at different cooling rates, the material properties also differ. As can be seen from the table, the greater the cooling rate, the better the material performance, the greater the first discharge capacity, and the higher the coulombic efficiency.
Table 2, summary of the results of the Performance tests of examples 1, 8 and 9
| Cooling rate/min | First discharge capacity mAh/g | First coulombic efficiency% |
| 5 | 229.4 | 76.2 |
| 20 | 252.0 | 79.8 |
| 100 | 272.8 | 82.2 |
Example 10:
this example prepares a cadmium doped lithium richManganese-based positive electrode material Li1.2Ni0.2Mn0.57Cd0.03O2。
According to the method of the embodiment 1, the yttrium source is changed to be added with 0.003mol of cadmium nitrate tetrahydrate, and other components are unchanged, so that the cadmium-doped lithium-rich manganese-based cathode material Li is prepared1.2Ni0.2Mn0.57Cd0.03O2Mixing the raw materials, adding 50mL of ethanol solution, putting the mixture into a water bath for heating, continuously stirring until the mixture is fully dissolved and mixed, putting the liquid into a drying box for evaporation drying, putting the dried material into a tubular furnace, heating the dried material from room temperature to 450 ℃ at the speed of 5 ℃/min, presintering the dried material at a low temperature for 1 hour, heating the dried material to 900 ℃ at the speed of 5 ℃/min, continuously calcining the dried material for 12 hours, taking the dried material out of the furnace, and rapidly cooling the calcined material to obtain the yttrium-doped lithium-rich manganese-based anode material.
The lithium ion battery is prepared from the prepared anode material, and the method comprises the following specific steps: mixing the lithium-rich manganese-based positive electrode material prepared in the embodiment 10, super P, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode piece; and then, assembling the lithium sheet serving as a negative electrode sheet and a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1: 1) serving as electrolyte in a glove box to obtain the lithium ion button cell.
And (3) carrying out cycle performance test on the lithium ion battery by using an electrochemical tester, wherein the test temperature is 25 ℃, the first charge and discharge performance of the battery is tested when the current density is 0.1C (1C is 200mA/g) and the charge and discharge voltage range is 2.0-4.8V. The multiplying power performance of the battery is tested under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C and 3C, the battery is activated for three weeks under the current density of 2.0-4.8V and 0.1C, and the cycle performance of the battery is tested within the voltage range of 2.0-4.8V.
Fig. 2 is an XRD analysis of the above examples 1-5, which shows that the sample patterns of the examples are similar, and all are typical lithium-rich manganese-based layered structures, indicating that the total structure of the material is not changed by doping 4 kinds of yttrium with different amounts. The intensity ratio of the 003 peak to the 104 peak in the figure represents the degree of cation shuffling in the layered structure, and when the yttrium content is 0.03, the ratio reaches a maximum of 1.42, and the degree of shuffling is the lowest.
FIG. 3 shows the cycling performance of batteries made from the materials of examples 1-5. The first discharge capacity of example 2 without doping was maximum and 272.3mAh/g, the discharge capacity fading after 100 cycles of charge and discharge was 203.5mAh/g, the capacity fading after 100 cycles was 74.7%, while the capacity fading the least was example 1, the fading from the first discharge was 255.2mAh/g and 230.4mAh/g, and the 100 cycles capacity remained at 90.3%. The capacity remained 81.2% after 100 cycles for example 3, 86.1% for example 4, and 88.6% for example 5.
Fig. 4 is a comparison of the rate capability of examples 1 and 2 and example 10, and it is evident that, in the case of high rate, yttrium doping when x is 0.03 can improve the capacity, while cadmium doping can also improve the rate capability by a suitable amount, and although the cadmium ion radius is larger than that of yttrium (cadmium ion radius is 97pm, and yttrium ion radius is 90pm), in the case of high rate, the cadmium lifting effect is not as good as that of yttrium, which means that the effect is not as good as the effect is larger than that of yttrium.
Fig. 5 is a comparison of the capacity cycling decay of example 1 and example 10, and it is evident that the decay inhibition effect of yttrium element on the capacity of the material is better during 100 cycles.
Example 11:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of the embodiment are basically the same as those of the embodiment 1, except that the raw materials comprise 0.126mol of lithium nitrate, 0.057mol of manganese nitrate, 0.020mol of nickel acetate and 0.003mol of yttrium acetate; the solvent is propanol, the mixture is dissolved and dried, then the mixture is put into a tube furnace to be preheated for 2 hours at the low temperature of 350 ℃ at the speed of 1 ℃/min, then the mixture is heated to 825 ℃ at the speed of 1 ℃/min to be continuously calcined for 11 hours, and the yttrium-doped lithium-rich manganese-based anode material is obtained after cooling and assembled into a battery.
The structure of the cathode material prepared in this example and the performance of the assembled battery were the same as those of example 1.
Example 12:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of the embodiment are basically the same as those of the embodiment 1, except that the raw materials comprise 0.126mol of lithium nitrate, 0.057mol of manganese nitrate, 0.020mol of nickel acetate and 0.003mol of yttrium acetate; the solvent is propanol, the mixture is dissolved and dried, then the mixture is put into a tube furnace to be heated to 550 ℃ at the speed of 3 ℃/min for low-temperature presintering for 1.5 hours, then the mixture is heated to 800 ℃ at the speed of 3 ℃/min for continuous calcining for 13 hours, and the yttrium-doped lithium-rich manganese-based positive electrode material is obtained after cooling and assembled into a battery.
The structure of the cathode material prepared in this example and the performance of the assembled battery were the same as those of example 1.
Example 13:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of this example are substantially the same as those of example 1 except that the raw materials are 0.126mol of lithium carbonate, 0.057mol of manganese carbonate, 0.020mol of nickel carbonate, and 0.003mol of yttrium nitrate hexahydrate; dissolving and drying isopropanol serving as a solvent, placing the mixture into a tubular furnace, heating the mixture to 500 ℃ at the speed of 8 ℃/min, presintering the mixture for 2 hours at a low temperature, heating the mixture to 925 ℃ at the speed of 8 ℃/min, continuously calcining the mixture for 14 hours, cooling the calcined mixture to obtain the yttrium-doped lithium-rich manganese-based positive electrode material, and assembling the yttrium-doped lithium-rich manganese-based positive electrode material into a battery.
The structure of the cathode material prepared in this example and the performance of the assembled battery were the same as those of example 1.
Example 14:
this example prepares a yttrium-doped lithium-rich manganese-based cathode material Li1.2Ni0.2Mn0.57Y0.03O2。
The preparation method and the steps of this example are substantially the same as those of example 1 except that the raw materials are 0.126mol of lithium carbonate, 0.057mol of manganese carbonate, 0.020mol of nickel carbonate, and 0.003mol of yttrium nitrate hexahydrate; dissolving and drying isopropanol serving as a solvent, placing the solution into a tubular furnace, heating the solution to 500 ℃ at the speed of 10 ℃/min, presintering the solution for 2 hours at a low temperature, heating the solution to 900 ℃ at the speed of 10 ℃/min, continuously calcining the solution for 15 hours, cooling the solution to obtain the yttrium-doped lithium-rich manganese-based positive electrode material, and assembling the yttrium-doped lithium-rich manganese-based positive electrode material into a battery.
The structure of the cathode material prepared in this example and the performance of the assembled battery were the same as those of example 1.
Claims (9)
1. An yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material is characterized in that: the anode material is a layered material with a chemical general formula of Li1.2Ni0.2Mn0.6-xYxO2Wherein x is more than 0 and less than or equal to 0.04.
2. The yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material according to claim 1, characterized in that: in the chemical general formula, x is more than or equal to 0.02 and less than or equal to 0.04.
3. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 1, characterized by comprising the following steps:
(1) adding a lithium source, a nickel source, a manganese source and an yttrium source into an alcohol solvent, dissolving and mixing to obtain a metal salt solution, and drying the metal salt solution to obtain an intermediate;
(2) heating and sintering the intermediate to obtain a sintered product;
(3) and cooling the sintered product to obtain the yttrium-doped lithium-rich manganese-based positive electrode material.
4. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 3, characterized in that: the heating sintering comprises low-temperature presintering and high-temperature heating, wherein the low-temperature presintering temperature is 350-550 ℃, and the low-temperature presintering time is 1-2 hours; the high-temperature heating temperature is 800-950 ℃, and the high-temperature heating time is 11-15 hours.
5. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 4, characterized in that: raising the temperature from room temperature to 350-550 ℃ at the speed of 1-10 ℃/min for low-temperature presintering, and then raising the temperature to 800-950 ℃ at the speed of 1-10 ℃/min for high-temperature heating.
6. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 3, characterized in that: the lithium source is at least one of lithium acetate dihydrate, lithium nitrate or lithium carbonate; the nickel source is at least one of nickel nitrate hexahydrate, nickel acetate or nickel carbonate; the manganese source is at least one of tetrahydrate manganese acetate, manganese nitrate or manganese carbonate; the yttrium source is at least one of yttrium nitrate hexahydrate or yttrium acetate.
7. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 3, characterized in that: the alcohol solvent is at least one of ethanol, propanol or isopropanol.
8. The preparation method of the yttrium-doped lithium-rich manganese-based lithium ion battery cathode material according to claim 3, characterized in that: the cooling is performed by liquid nitrogen.
9. A lithium ion battery comprising a positive electrode, characterized in that: the positive electrode comprises the yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material of claim 1 or 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437288A (en) * | 2021-06-29 | 2021-09-24 | 贝特瑞（江苏）新材料科技有限公司 | Positive electrode active material, preparation method thereof and lithium ion battery |
| CN114156481A (en) * | 2021-12-01 | 2022-03-08 | 西安交通大学 | Atomic-level doped lithium nickel manganese oxide positive electrode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979549A (en) * | 2015-07-29 | 2015-10-14 | 杭州朗鑫新材料科技有限公司 | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material |
-
2019
- 2019-12-19 CN CN201911315922.0A patent/CN111082044A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979549A (en) * | 2015-07-29 | 2015-10-14 | 杭州朗鑫新材料科技有限公司 | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material |
Non-Patent Citations (1)
| Title |
|---|
| NING LI等: ""The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries"", 《J. MATER. CHEM. A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437288A (en) * | 2021-06-29 | 2021-09-24 | 贝特瑞（江苏）新材料科技有限公司 | Positive electrode active material, preparation method thereof and lithium ion battery |
| CN114156481A (en) * | 2021-12-01 | 2022-03-08 | 西安交通大学 | Atomic-level doped lithium nickel manganese oxide positive electrode material and preparation method and application thereof |
| CN114156481B (en) * | 2021-12-01 | 2023-04-07 | 西安交通大学 | Atomic-level doped lithium nickel manganese oxide positive electrode material and preparation method and application thereof |
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Application publication date: 20200428 |