CN111458367A - Novel method for predicting structure of lithium-rich material - Google Patents

Novel method for predicting structure of lithium-rich material Download PDF

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CN111458367A
CN111458367A CN202010319322.8A CN202010319322A CN111458367A CN 111458367 A CN111458367 A CN 111458367A CN 202010319322 A CN202010319322 A CN 202010319322A CN 111458367 A CN111458367 A CN 111458367A
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lithium
rich material
sample
predicting
specific heat
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CN111458367B (en
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李广社
冯涛
李莉萍
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Jilin University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/005—Investigating or analyzing materials by the use of thermal means by investigating specific heat
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a novel method capable of predicting a lithium-rich material structure, which comprises the steps of putting a lithium-rich material into an oven to be dried for 4 hours at 90 ℃ to remove surface adsorbed water, then weighing about 15mg of a powder sample, and pressurizing the powder sample by using a die with the diameter of 3mm, wherein the pressure is set to be 6MPa, the pressurizing duration is 1min, and thus a cylindrical sample with the diameter of 3mm is obtained. And then measuring the specific heat of the cylindrical sample by using a comprehensive physical property measuring system, wherein the measuring temperature range is 2-300K, the thermal process is heating measurement, the measuring interval is below 200K and is logarithmic interval, and a point is measured every 10K above 200K. And finally, comparing the measurement result with the specific heat of the standard sample, and further judging whether the lithium-rich material is a solid solution, a composite or a mixed form of the solid solution and the composite. Compared with a transmission electron microscope, the method is simpler, more comprehensive and more accurate, and has important significance for promoting the research of the lithium-rich material structure and realizing the performance optimization based on the structure regulation.

Description

Novel method for predicting structure of lithium-rich material
Technical Field
The invention relates to the field of structural research of lithium ion battery anode materials, in particular to a method for judging whether a lithium-rich material structure is a solid solution or a composite.
Background
With the wide application of lithium ion batteries, the public requirements for the anode materials of the lithium ion batteries are higher and higher, such as high capacity, high safety, good cycle stability, good rate capability and the like, the common ternary materials in the current market do not have a large space for further improving the capacity, the capacity of the lithium-rich layered transition metal oxide can easily reach more than 200mAh/g, even can reach 300mAh/g, and can bring huge improvement of energy density for the lithium ion batteries, therefore, the lithium-rich material x L i2MnO3·(1-x)LiMO2(M ═ Mn, Co, Ni, and the like) is one of the most promising positive electrode materials for next-generation high energy density lithium ion batteries, and is now a research focus for positive electrode materials, and also has an advantage of low cost.
The lithium-rich cathode material has three possible structures, namely L i2MnO3And L iMO2The composite is formed by two substances, the second is a solid solution formed by the two substances after being dissolved with each other, and the third is a structure in which the composite and the solid solution coexist. It is generally considered that when the structure of the lithium-rich material is in a partial solid solution, the lithium ion battery composed of the lithium-rich material as the positive electrode has higher specific capacity. However, at present, the judgment of the crystal structure of the lithium-rich material still has difficulty, and a unified judgment standard cannot be given through XRD and a transmission electron microscope, so that the research on the structure-activity relationship between the structure and the performance of the lithium-rich material is not facilitated, and the solution of the application problem of the lithium-rich material is also not facilitated. Therefore, there is an urgent need to develop a new method for judging the crystal structure of lithium-rich material, and to predict thisWhether the structure of the material-like material is a composite or a solid solution provides reference.
Disclosure of Invention
The present invention is directed to solving the above problems by providing a novel method for predicting the crystal structure of a lithium-rich material. The rationale is that lithium-rich materials with solid solution structures tend to exhibit a higher disorder of their internal atomic arrangement and therefore should have a larger entropy value and the reaction should have a higher value of specific heat in specific heat. Based on this, we can make a judgment on the crystal structure of the lithium-rich material by measuring the specific heat of the material and comparing it with a standard sample.
The invention achieves the above purpose through the following technical scheme:
the method specifically comprises the following steps:
(1) and (4) putting the lithium-rich material into an oven for drying.
(2) And measuring the specific heat of the dried sample by using a comprehensive physical property measuring system.
(3) Comparing the specific heat of the lithium-rich material with the specific heat of a standard sample so as to judge the structure type of the lithium-rich material;
preferably, the temperature of the oven in the step (1) is in the range of 80-150 ℃; the time range is 2-5 h.
Preferably, the mass of the test sample in step (2) does not exceed 15 mg; the specific heat test temperature range is 2-300K.
The invention has the beneficial effects that:
compared with the traditional transmission electron microscope technology, the method provided by the invention is a simpler, comprehensive and accurate judgment method, breaks through the limitation that the transmission electron microscope technology can only detect local areas, and has important significance for promoting the research of the lithium-rich material structure and realizing performance optimization based on structure regulation.
Drawings
FIG. 1 is a graph of specific heat data for all lithium rich materials of the examples.
FIG. 2 is a graph of the specific capacity of all lithium rich materials of the examples.
Detailed Description
The invention will be further described with reference to the accompanying drawings in which:
the invention utilizes the comprehensive physical property measuring system-9T of the American Quantum design company to measure heat; the measurements were performed on the comparative capacities at the electrochemical workstation CHI660 of Shanghai Chenghua Co.
Example 1 Co-precipitation preparation of lithium-rich Material L i1.2Ni0.133Co0.133Mn0.533O2Crystal structure judgment of
The lithium-rich material L i prepared by the coprecipitation method1.2Ni0.133Co0.133Mn0.533O2Drying at 90 ℃ in an oven for 4h to remove surface adsorbed water, weighing about 15mg of powder sample, pressurizing the powder sample by using a mold with the diameter of 3mm, setting the pressure to be 6MPa, and pressurizing for 1min to obtain a cylindrical sample with the diameter of 3mm, measuring the specific heat of the cylindrical sample by using a comprehensive physical property measurement system, wherein the measurement temperature range is 2-300K, the thermal process is heating measurement, the measurement interval is below 200K and is logarithmic interval, a point is measured every 10K above 200K, the measurement result is shown in figure 1, measuring the specific capacity of the sample by using an electrochemical workstation, and preparing a lithium-rich material L i prepared by a coprecipitation method1.2Ni0.133Co0.133Mn0.533O2After the lithium ion battery is assembled as the anode, the current density of 100mA/g is measured in a voltage range of 3.0-4.6V, the number of cycles is 20, and the measurement result is shown in figure 2. From fig. 1, we can see that the specific heat of the sample prepared by the co-precipitation method is between the highest standard sample and the lowest standard sample, so the structure thereof should belong to the structure in which the third compound and the solid solution coexist, but the solid solution degree thereof is obviously higher than the samples synthesized by other methods, which is also confirmed by the test result of the specific capacity of fig. 2, because the lithium-rich material with higher solid solution degree constitutes the battery with higher specific capacity.
Example 2 Solvothermally prepared lithium-rich material L i1.2Ni0.133Co0.133Mn0.533O2Crystal structure judgment of
The lithium-rich material L i prepared by the solvothermal method1.2Ni0.133Co0.133Mn0.533O2Drying at 90 ℃ in an oven for 4h to remove surface adsorbed water, weighing about 15mg of powder sample, pressurizing the powder sample by using a mold with the diameter of 3mm, setting the pressure to be 6MPa, and pressurizing for 1min to obtain a cylindrical sample with the diameter of 3mm, measuring the specific heat of the cylindrical sample by using a comprehensive physical property measurement system, wherein the measurement temperature range is 2-300K, the thermal process is temperature rise measurement, the measurement interval is below 200K and is logarithmic interval, a point is measured every 10K above 200K, the measurement result is shown in figure 1, measuring the specific capacity of the sample by using an electrochemical workstation, and preparing a lithium-rich material L i prepared by a solvothermal method1.2Ni0.133Co0.133Mn0.533O2After the lithium ion battery is assembled as the anode, the current density of 100mA/g is measured in a voltage range of 3.0-4.6V, the number of cycles is 20, and the measurement result is shown in figure 2. It can be seen from fig. 1 that the specific heat of the sample prepared by the solvothermal method is between the highest standard sample and the lowest standard sample, so the structure thereof should belong to the structure in which the third compound and the solid solution coexist, but the solid solution degree thereof should be lower than that of the lithium-rich material prepared by the co-precipitation method, which is also confirmed by the specific capacity test result of fig. 2, because the specific capacity of the lithium-rich material prepared by the solvothermal method is lower than that of the lithium-rich material prepared by the co-precipitation method.
EXAMPLE 3 solid phase preparation of lithium-rich Material L i1.2Ni0.133Co0.133Mn0.533O2Crystal structure judgment of
Preparing lithium-rich material L i by solid phase method1.2Ni0.133Co0.133Mn0.533O2Drying at 90 deg.C for 4 hr to remove surface adsorbed water, weighing about 15mg powder sample, and pressurizing with a mold with diameter of 3mm under 6MPa for 1min to obtain cylindrical sample with diameter of 3 mm. Then measuring the specific heat of the cylindrical sample by using a comprehensive physical property measuring system, wherein the measuring temperature range is 2-300K, and the heat isThe process is temperature rise measurement, the measurement interval is logarithmic interval below 200K, a point is measured every 10K above 200K, the measurement result is shown in figure 1, the specific capacity of a sample is measured by an electrochemical workstation, and the lithium-rich material L i prepared by a solid phase method is used1.2Ni0.133Co0.133Mn0.533O2After the lithium ion battery is assembled as the anode, the current density of 100mA/g is measured in a voltage range of 3.0-4.6V, the number of cycles is 20, and the measurement result is shown in figure 2. It can be seen from fig. 1 that the specific heat of the sample prepared by the solid phase method is between the highest standard sample and the lowest standard sample, so the structure thereof should belong to the structure in which the third compound and the solid solution coexist, but the solid solution degree thereof should be lower than that of the two lithium-rich materials prepared by the co-precipitation method and the solvothermal method, which is also confirmed by the specific capacity test result of fig. 2, because the specific capacity of the lithium-rich material prepared by the solid phase method is lower than that of the lithium-rich material prepared by the co-precipitation method and the solvothermal method.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. A new method for predicting the structure of a lithium-rich material is characterized in that: the method comprises the following steps:
(1) mixing lithium-rich material L i1.2Ni0.133Co0.133Mn0.533O2Drying in a drying oven;
(2) measuring the specific heat of the dried sample by using a comprehensive physical property measuring system;
(3) and (3) comparing the specific heat data obtained in the step (2) with the specific heat of the standard sample to judge the structure type and the structure solid solution degree of the lithium-rich material.
2. The method of predicting the structure of a lithium-rich material of claim 1, wherein: the temperature range of the oven in the step (1) is 80-150 ℃; the time range is 2-5 h.
3. The method of predicting the structure of a lithium-rich material of claim 1, wherein: step (2), the mass of a test sample is not more than 15 mg; the powder sample was pressurized with a die having a diameter of 3mm, the pressure being set at 6MPa and the duration of the pressurization being 1 min.
4. The method of predicting the structure of a lithium-rich material of claim 1, wherein: the measurement temperature range is 2-300K, the thermal process is heating measurement, the measurement interval is below 200K and is logarithmic interval, and a point is measured every 10K above 200K.
5. The method of predicting the structure of a lithium-rich material of claim 1, wherein: the standard sample in the step (3) should be a sample of a pure solid solution structure and a sample of a pure composite structure.
6. The method of claim 1, wherein the lithium rich material L i is selected from the group consisting of Li-rich material1.2Ni0.133Co0.133Mn0.533O2Is prepared by one of coprecipitation method, solvothermal method, thermal injection method, hydrothermal method and solid phase method.
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Citations (5)

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US5711604A (en) * 1993-12-14 1998-01-27 Seiko Instruments Inc. Method for measuring the coefficient of heat conductivity of a sample
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CN102875130A (en) * 2012-10-15 2013-01-16 福建师范大学 Method for preparing doped lithium-enriched solid solution cathode material by using carbon-added compound

Patent Citations (5)

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US5711604A (en) * 1993-12-14 1998-01-27 Seiko Instruments Inc. Method for measuring the coefficient of heat conductivity of a sample
JPH09222404A (en) * 1996-02-19 1997-08-26 Agency Of Ind Science & Technol Method and device for measuring specific heat capacity
JP2003344324A (en) * 2002-05-24 2003-12-03 Keio Gijuku Isopiestic specific heat measurement method and apparatus therefor for high pressure fluid
US20120156566A1 (en) * 2009-06-24 2012-06-21 Reminex Sa Particles of doped lithium cobalt oxide, method for preparing the same and their use in lithium ion batteries
CN102875130A (en) * 2012-10-15 2013-01-16 福建师范大学 Method for preparing doped lithium-enriched solid solution cathode material by using carbon-added compound

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