CN109956505B - Lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents
Lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109956505B CN109956505B CN201910277165.6A CN201910277165A CN109956505B CN 109956505 B CN109956505 B CN 109956505B CN 201910277165 A CN201910277165 A CN 201910277165A CN 109956505 B CN109956505 B CN 109956505B
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- rich manganese
- electrode material
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention discloses a lithium-rich manganese-based positive electrode material and a preparation method and application thereof, wherein the lithium-rich manganese-based positive electrode material is a flexible lithium-rich manganese-based positive electrode material and does not contain other inert components, so that the energy density of the material is obviously improved; the method can control the thickness and flexibility of the product film by controlling the coating amount and the vacuum drying condition.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a lithium-rich manganese-based positive electrode material and a preparation method and application thereof.
Background
In recent years, flexible electronic devices such as a windable liquid crystal display screen, wearable communication equipment, intelligent glasses, a bracelet, a watch, a flexible electronic strain sensor, a flexible electronic skin and the like are increasingly popular, great changes are brought to daily life of people, application scope of the electronic devices is widened, and the application fields (such as scroll type, folding type and stretching type electronic products) which are beyond the power of the electronic equipment of "hard nation" before touch are attracted to, and the worldwide attention is attracted and the development is rapid. It is conceivable that the flexible electronic device will deeply affect and change people's living habits and working modes like the existing smart phone and mobile internet.
The lithium ion battery has the characteristics of high energy density, high voltage, good cyclicity, low self-discharge rate, no memory effect and the like, can meet the requirements of miniaturization, light weight, high energy and shape diversification of a chemical power supply, and the lithium-rich manganese-based anode material has about twice of the actual discharge specific capacity of the current mainstream anode material; in addition, the content of Mn element in the material is larger, so that the material and LiCoO are mixed2Compared with nickel-cobalt-manganese ternary electrode material, the material has low costThe lithium-rich manganese-based anode material is low in cost, the safety is greatly improved, and the lithium-rich manganese-based anode material is considered as an ideal choice for the next generation of lithium ion battery anode materials.
In principle, flexible batteries need to meet the requirements of external deformation and also be able to withstand the volume changes inside the battery during charging and discharging. Therefore, the ideal flexible battery material needs to have both conductive flexibility and mechanical flexibility. The flexible lithium ion battery is required to still maintain excellent mechanical and electrical properties under the repeated deformation condition, and the development of a high-performance flexible electrode is a key and difficult point. Most inorganic electrode materials are granular, have poor mechanical properties, are not easy to deform, are difficult to directly construct a flexible electrode, and are often required to be compounded with a flexible substrate with good mechanical properties and high conductivity, such as carbon materials, conductive fabrics and the like. Generally, a flexible electrode is manufactured by coating a slurry containing an electrode active material, a conductive agent and a binder on a flexible conductive substrate, such as plastic, paper, carbon nanotubes, etc.
CN106207091A discloses a flexible positive electrode of a lithium ion battery, a preparation method thereof and an ultra-flexible lithium ion full battery, which specifically comprises the following steps: 1) selecting a flexible framework, and depositing a manganese oxyhydroxide material on the flexible framework in an electroplating way; 2) the electrodeposited manganese oxyhydroxide material is lithiated in low-melting-point lithium ion-containing molten salt to form lithium manganate which is a lithium ion battery positive electrode material conformally grown on a flexible framework.
CN103825007B discloses a preparation method for constructing a phosphate flexible lithium ion secondary battery positive electrode based on a graphene-carbon nanotube composite structure, which is simple and easy to implement, but uses many inert components that do not contribute to capacity, and the "rigid" active material is not mechanically matched with the "flexible" conductive substrate, and the contact between the active material and the current collector is not sufficient.
Although the above documents disclose some flexible cathode materials and methods for preparing the same, there is a problem that an inert component which does not contribute to capacity needs to be added during the preparation process, resulting in low battery capacity, and therefore, it is still of great significance to develop a flexible cathode material which is simple in preparation process and does not contain an inert component in the cathode material.
Disclosure of Invention
The invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium-rich manganese-based positive electrode material, which is a flexible lithium-rich manganese-based positive electrode material.
The invention discloses a lithium-rich manganese-based positive electrode material, which is a flexible lithium-rich manganese-based positive electrode material, wherein the material does not contain an inert component, so that the energy density of the flexible positive electrode material is obviously improved.
Preferably, the cathode material is of a thin film structure.
Preferably, the positive electrode material is a self-supporting thin film structure.
Preferably, the membrane has a support membrane area of 0.1-50cm2E.g. 0.1cm2、1cm2、5cm2、10cm2、20cm2、30cm2、40cm2Or 50cm2And the like.
Preferably, the thin film has a support film thickness of 1-30 μm, such as 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the like.
Preferably, the general molecular formula of the lithium-rich manganese-based cathode material is Li1+c[Mn1-a-bNiaCob]1-cO2Wherein, 0<c≤0.5；0<a<1，0≤b<1。
In a second aspect, a method for preparing a lithium-rich manganese-based positive electrode material according to the first aspect, the method comprising the steps of:
(1) mixing a manganese-based material with a lithium source, and calcining to obtain a lithium-rich manganese-based material intermediate;
(2) mixing the lithium-rich manganese-based material intermediate obtained in the step (1) with stripping liquid, carrying out stripping treatment, and centrifuging to obtain a suspension of the lithium-rich manganese-based material;
(3) And (3) coating the suspension liquid obtained in the step (2) on a substrate, and drying to obtain the lithium-rich manganese-based positive electrode material.
According to the method, a lithium source and a manganese-based material are mixed, a suspension of the lithium-rich manganese-based material is obtained after stripping and centrifugation, the suspension is coated on a substrate material and then dried to obtain the lithium-rich manganese-based anode material, and the solvent is evaporated in the drying process, so that the flexible lithium-rich manganese-based anode material with a thin film structure is obtained. Inert materials (binders and the like) which do not contribute to capacity do not need to be added in the preparation process, so that the energy density of the prepared lithium-rich manganese-based material is obviously improved, and the method provided by the invention is convenient for controlling the film thickness and flexibility of the product through the coating amount of the suspension and the drying condition.
Preferably, the preparation method of the manganese-based material of step (1) includes a coprecipitation method.
Preferably, the preparation method of the manganese-based material in the step (1) comprises the following steps:
(a) preparing a mixed solution containing a nickel source, a manganese salt and a cobalt salt;
(b) adding a precipitator into the mixed solution in the step (a), reacting, and drying to obtain the manganese-based material.
Preferably, the nickel source of step (a) comprises any one of nickel sulphate, nickel nitrate or nickel chloride or a mixture of at least two thereof.
Preferably, the source of manganese of step (a) comprises any one or a mixture of at least two of manganese sulphate, manganese nitrate or manganese chloride.
Preferably, the cobalt source of step (a) comprises any one of cobalt sulphate, cobalt nitrate or cobalt chloride, or a mixture of at least two thereof.
Preferably, the molar ratio of the nickel source, manganese source and cobalt source of step (a) is (1-a-b) a: b, wherein 0< a <1, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8 or 0.9, etc.; 0< b.ltoreq.1, for example 0.1, 0.2, 0.3, 0.5, 0.7 or 0.9 etc.
Preferably, the precipitant in step (b) includes any one or a mixture of at least two of sodium carbonate, potassium carbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide or urea, and the mixture exemplarily includes a mixture of sodium carbonate and potassium carbonate, a mixture of ammonium carbonate and ammonium bicarbonate or a mixture of sodium hydroxide, potassium hydroxide and urea, and the like.
Preferably, the temperature of the reaction of step (b) is 40-80 ℃, e.g. 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ etc.
Preferably, the step (b) further comprises adding a buffer to the reaction solution to adjust the pH of the solution.
Preferably, the buffer comprises urea and/or ammonia.
Preferably, the buffer is added such that the pH of the solution is 7-12, e.g. 7, 8, 9, 10, 11 or 12 etc.
Preferably, the drying temperature in step (b) is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, etc.
Preferably, the lithium source includes any one of lithium carbonate, lithium hydroxide or lithium nitrate or a mixture of at least two thereof, and the mixture exemplarily includes a mixture of lithium carbonate and lithium hydroxide, a mixture of lithium hydroxide and lithium nitrate, or a mixture of lithium carbonate and lithium nitrate, and the like.
Preferably, the ratio of the molar amount of lithium source to the total molar amount of metal elements in the manganese-based material in step (1) is (1+ c) to (1-c), wherein 0< c ≦ 0.5, such as 0.1, 0.2, 0.3, 0.4, or 0.5, and the like.
Preferably, the calcination of step (1) comprises a first calcination and a second calcination in sequence.
Preferably, the temperature of the first calcination is 350-650 ℃, such as 360 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 630 ℃, etc.
Preferably, the time of the first calcination is 2 to 10h, such as 2h, 4h, 6h, 8h or 9h, etc.
Preferably, the temperature of the second calcination is 800-.
Preferably, the time of the second calcination is 2 to 20h, such as 2h, 5h, 10h, 15h or 20h, etc.
Preferably, the atmosphere of the calcination in the step (1) is an oxygen-containing atmosphere.
Preferably, the stripping solution in step (2) comprises any one or a mixture of at least two of water, formamide, dimethylformamide or dimethylacetamide; the mixture illustratively includes a mixture of water and formamide, a mixture of dimethylformamide and dimethylacetamide, or a mixture of formamide and dimethylformamide, and the like.
Preferably, the method of the peeling treatment of step (2) includes an ultrasonic and/or heat treatment.
Preferably, the temperature of the heating treatment is 50-100 ℃; for example, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100 deg.C.
Preferably, the time of the stripping treatment in the step (2) is 2-10 h; for example, 2h, 4h, 6h, 8h, or 9h, etc.
Preferably, the rotation speed of the centrifugation in the step (2) is 1000-10000 r/min; for example 1000r/min, 2000r/min, 3000r/min, 5000r/min, 7000r/min or 9000r/min, etc.
Preferably, the centrifugation time of the step (2) is 10-60 min; for example, 10min, 20min, 30min, 40min, 50min or 60 min.
Preferably, the mass ratio of the lithium-rich manganese-based material intermediate to the stripping solution in the step (2) is (0.01-0.1): 1; e.g., 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1, or 0.09:1, etc.
Preferably, the suspension of the lithium-rich manganese-based material of step (2) is in a colloidal state.
Preferably, the concentration of the suspension of the lithium-rich manganese-based material of step (2) is 1-10 wt%, such as 1 wt%, 2 wt%, 3 wt%, 5 wt%, 7 wt%, or 9 wt%, etc.
Preferably, the substrate in step (3) comprises any one of polyethylene, polypropylene, polystyrene, mica, glass fiber or monocrystalline silicon or a mixture of at least two of the above.
Preferably, the base size of the substrate of step (3) is 10-50cm, such as 10cm, 20cm, 30cm, 40cm or 50cm, etc.
Preferably, the drying method in step (3) comprises vacuum drying.
Preferably, the temperature of the vacuum drying is 50-120 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 110 ℃ and the like.
Preferably, the vacuum drying time is 10-36h, such as 12h, 16h, 18h, 22h, 25h, 30h or 34h, etc.
The method controls the flexibility of the product film by controlling the vacuum drying condition and time, and the film prepared in the temperature range has better flexibility.
Preferably, the method further comprises stripping the lithium-rich manganese-based positive electrode material from the substrate.
As a preferable technical scheme of the invention, the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps:
(1') preparing a mixed solution containing a nickel source, manganese salt and cobalt salt, then adding a precipitator, reacting at 40-80 ℃, adding a buffer solution to adjust the pH value of the reaction solution to 7-12, and drying to obtain the manganese-based material; the molar ratio of the nickel source to the manganese source to the cobalt source is (1-a-b) a: b, wherein a is more than 0 and less than 1, and b is more than 0 and less than or equal to 1;
(2 ') mixing the manganese-based material obtained in the step (1') with a lithium source, and calcining to obtain a lithium-rich manganese-based material intermediate; the ratio of the molar weight of the lithium source to the total molar weight of the metal elements in the manganese-based material is (1+ c) to (1-c), wherein c is more than 0 and less than or equal to 0.5;
(3 ') mixing the lithium-rich manganese-based material intermediate obtained in the step (2') with stripping liquid, carrying out stripping treatment, and centrifuging to obtain a suspension of the lithium-rich manganese-based material, wherein the mass ratio of the lithium-rich manganese-based material intermediate to the stripping liquid is (0.01-0.1): 1;
(4 ') coating the suspension obtained in the step (3') on a substrate, and drying the substrate in vacuum at the temperature of between 50 and 120 ℃ for 10 to 36 hours to obtain the lithium-rich manganese-based positive electrode material.
In a third aspect, the present invention provides the use of the lithium-rich manganese-based positive electrode material according to the first aspect, for a positive electrode material for a lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lithium-rich manganese-based positive electrode material prepared by the method does not contain inert components which do not contribute to capacity, so that the energy density of the flexible positive electrode material is improved;
(2) according to the method, the thickness and flexibility of the flexible lithium-rich manganese-based positive electrode material are controlled by controlling the coating amount of the suspension of the lithium-rich manganese-based material and the vacuum drying condition;
(3) the preparation method of the invention is simple and is easy for industrial application.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Molecular formula is Li1.2Mn0.56Ni0.16Co0.08O2The preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1') preparing a mixed solution of nickel sulfate, manganese sulfate and cobalt sulfate with the total metal salt concentration of 2M, then adding a sodium hydroxide solution with the concentration of 2M, reacting at 55 ℃, adding ammonia water to adjust the pH value of the reaction solution to 10.5, and drying at 100 ℃ for 12 hours to obtain the manganese-based material; the molar ratio of the nickel sulfate to the manganese sulfate to the cobalt sulfate is 0.2:0.7: 0.1;
(2 ') mixing the manganese-based material obtained in the step (1') with a lithium source, performing two-step calcination, firstly calcining at 500 ℃ for 6 hours, and then calcining at 850 ℃ for 20 hours to obtain a lithium-rich manganese-based material intermediate; the lithium source is lithium carbonate, and the addition amount of the lithium source is 5 mol% more than the theoretical addition amount of the lithium source;
(3 ') mixing the lithium-rich manganese-based material intermediate obtained in the step (2') with formamide, carrying out ultrasonic treatment for 10 hours, centrifuging at 5000r/min for 100 minutes, taking the upper-layer liquid to obtain a suspension of the lithium-rich manganese-based material, wherein the mass ratio of the lithium-rich manganese-based material intermediate to the stripping liquid is 0.1: 1;
(4 ') diluting the suspension obtained in the step (3') to 8 wt%, coating the diluted suspension on a culture dish containing polyethylene with a basic size of 50cm, performing nitrogen purging, performing vacuum drying at 60 ℃ for 10h, immersing the dried suspension in acetone, and performing vacuum drying to obtain the lithium-rich manganese-based cathode material.
Example 2
Molecular formula is Li1.2Mn0.64Ni0.08Co0.08O2The preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1') preparing a mixed solution of nickel chloride, manganese chloride and cobalt chloride with the total metal salt concentration of 2M, then adding a sodium carbonate solution with the concentration of 1M, reacting at 55 ℃, adding ammonia water to adjust the pH value of the reaction solution to 8, and drying at 100 ℃ for 12 hours to obtain the manganese-based material; the molar ratio of the nickel chloride to the manganese chloride to the cobalt chloride is 0.1:0.8: 0.1;
(2 ') mixing the manganese-based material obtained in the step (1') with a lithium source, performing two-step calcination, firstly calcining at 550 ℃ for 6 hours, and then calcining at 950 ℃ for 20 hours to obtain a lithium-rich manganese-based material intermediate; the lithium source is lithium carbonate, and the addition amount of the lithium source is 10 mol% more than the theoretical addition amount of the lithium source;
(3 ') mixing the lithium-rich manganese-based material intermediate obtained in the step (2') with formamide, carrying out ultrasonic treatment for 5 hours, centrifuging at 10000r/min for 60 minutes, taking the upper-layer liquid to obtain a suspension of the lithium-rich manganese-based material, wherein the mass ratio of the lithium-rich manganese-based material intermediate to a stripping liquid is 0.01: 1;
(4 ') diluting the suspension obtained in the step (3') to 1 wt%, coating the diluted suspension on a culture dish containing polypropylene with a basic size of 30cm, performing nitrogen purging, performing vacuum drying at 80 ℃ for 20h, immersing the dried suspension in acetone, and performing vacuum drying to obtain the lithium-rich manganese-based cathode material.
Example 3
Molecular formula is Li1.2Mn0.32Ni0.32Co0.16O2The preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
(1') preparing a mixed solution of nickel nitrate, manganese nitrate and cobalt nitrate with the total metal salt concentration of 2M, then adding a sodium carbonate solution with the concentration of 1M, reacting at the temperature of 60 ℃, adding ammonia water to adjust the pH value of the reaction solution to 8, and drying at the temperature of 100 ℃ for 12 hours to obtain the manganese-based material; the molar ratio of the nickel nitrate to the manganese nitrate to the cobalt nitrate is 0.4:0.4: 0.2;
(2 ') mixing the manganese-based material obtained in the step (1') with a lithium source, performing two-step calcination, firstly calcining at 450 ℃ for 6 hours, and then calcining at 800 ℃ for 20 hours to obtain a lithium-rich manganese-based material intermediate; the lithium source is LiOH, and the addition amount of the lithium source is 20 mol% more than the theoretical addition amount of the lithium source.
(3 ') mixing the lithium-rich manganese-based material intermediate obtained in the step (2') with formamide, carrying out ultrasonic treatment for 10 hours, centrifuging at 10000r/min for 120 minutes, taking the upper-layer liquid to obtain a suspension of the lithium-rich manganese-based material, wherein the mass ratio of the lithium-rich manganese-based material intermediate to a stripping liquid is 0.06: 1;
(4 ') diluting the suspension obtained in the step (3') to 5 wt%, coating the diluted suspension on a mica culture dish with a basic size of 20cm, performing nitrogen purging, performing vacuum drying at 60 ℃ for 10h, immersing the dried suspension in acetone, and performing vacuum drying to obtain the lithium-rich manganese-based positive electrode material.
Example 4
In this example, the mass ratio of the lithium-rich manganese-based material intermediate to the stripping solution in example 1 was changed to 0.01:1, and the other conditions were completely the same as those in example 1.
Example 5
This example differs from example 1 in that the suspension of step (3') is diluted to 5% by weight, otherwise the conditions are exactly the same as in example 1.
Example 6
This example differs from example 1 in that the vacuum drying temperature in step (4') was replaced with 100 ℃; other conditions were exactly the same as in example 1.
Example 7
This example replaces the same amount of formamide in example 1 with dimethylformamide, and the other conditions are exactly the same as in example 1.
Example 8
This example differs from example 1 in that the vacuum drying time in step (4') was replaced with 30 h; other conditions were exactly the same as in example 1.
Example 9
This example replaces the substrate of example 1 with polystyrene, and the other conditions are exactly the same as compared to example 1.
Example 10
In this example, the substrate in example 1 was replaced with single crystal silicon, and the other conditions were exactly the same as in example 1.
Example 11
This example replaces the base size of the substrate in example 1 with 10cm, and the other conditions are exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that the vacuum drying temperature in step (4') was replaced with 40 ℃; other conditions were exactly the same as in example 1.
Comparative example 2
In the comparative example, the mass ratio of the lithium-rich manganese-based material intermediate to the stripping solution in example 1 was changed to 0.001:1, and the other conditions were completely the same as those in example 1.
Comparative example 3
This comparative example differs from example 1 in that the suspension of step (3') is diluted to 15% by weight, otherwise exactly the same conditions are used as compared to example 1.
Comparative example 4
This comparative example differs from example 1 in that the suspension of step (3') is diluted to 0.1% by weight, otherwise exactly the same conditions are used as compared to example 1.
Comparative example 5
This example replaces the base size of the substrate in example 1 with 60cm, and the other conditions are exactly the same as in example 1.
Performance test conditions:
preparing the positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 5 into a soft package battery, testing the prepared battery on a novyi battery testing system under a normal temperature condition, wherein a charging and discharging voltage interval is 2-4.8V, a charging and discharging rate is 0.1C, and a cycle capacity retention ratio of 100 weeks is 100 th charging specific capacity/first charging specific capacity; the test results are shown in Table 1.
TABLE 1
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (35)
1. The preparation method of the lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) mixing a manganese-based material with a lithium source, and calcining to obtain a lithium-rich manganese-based material intermediate;
(2) mixing the lithium-rich manganese-based material intermediate obtained in the step (1) with stripping liquid, carrying out stripping treatment, and centrifuging to obtain a suspension of the lithium-rich manganese-based material;
(3) coating the suspension liquid obtained in the step (2) on a substrate, and drying to obtain the lithium-rich manganese-based positive electrode material;
the stripping solution in the step (2) comprises any one or a mixture of at least two of formamide, dimethylformamide or dimethylacetamide; the stripping treatment method in the step (2) comprises ultrasonic treatment and/or heating treatment; the mass ratio of the lithium-rich manganese-based material intermediate to the stripping liquid in the step (2) is (0.01-0.1): 1; the substrate in the step (3) comprises any one or a mixture of at least two of polyethylene, polypropylene, polystyrene, mica, glass fiber or monocrystalline silicon; the basic size of the substrate in the step (3) is 10-50 cm; the lithium-rich manganese-based positive electrode material is a flexible lithium-rich manganese-based positive electrode material.
2. The method for preparing the lithium-rich manganese-based positive electrode material according to claim 1, wherein the positive electrode material has a thin film structure.
3. The method of claim 2, wherein the positive electrode material is in a self-supporting film structure.
4. The method for preparing the lithium-rich manganese-based positive electrode material according to claim 2, wherein the thin film has a support film area of 0.1-50cm2。
5. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 2, wherein the thickness of the support film of said thin film is 1 to 30 μm.
6. The method for preparing the lithium-rich manganese-based positive electrode material according to claim 1, wherein the general molecular formula of the lithium-rich manganese-based positive electrode material is Li1+c[Mn1-a-bNiaCob]1-cO2Wherein, 0<c≤0.5；0<a<1，0≤b<1。
7. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the method for preparing the manganese-based material of step (1) comprises a coprecipitation method.
8. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 6, wherein the method for preparing a manganese-based material according to step (1) comprises the steps of:
(a) preparing a mixed solution containing a nickel source, a manganese salt and a cobalt salt;
(b) adding a precipitator into the mixed solution in the step (a), reacting, and drying to obtain the manganese-based material.
9. The method for preparing the lithium-rich manganese-based positive electrode material according to claim 8, wherein the molar ratio of the nickel source, the manganese source and the cobalt source in step (a) is (1-a-b): a: b, wherein 0< a <1, and 0< b < 1.
10. The method of claim 8, wherein the precipitant in step (b) comprises any one or a mixture of at least two of sodium carbonate, potassium carbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, or urea.
11. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 8, wherein the temperature of the reaction in step (b) is 40 to 80 ℃.
12. The method of claim 8, wherein the step (b) further comprises adding a buffer to the reaction solution to adjust the pH of the solution.
13. The method of claim 12, wherein the buffer comprises urea and/or ammonia.
14. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 12, wherein the buffer is added so that the pH of the solution is 7 to 12.
15. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 8, wherein the drying temperature in step (b) is 80 to 120 ℃.
16. The method of claim 1, wherein the lithium source comprises any one of lithium carbonate, lithium hydroxide, or lithium nitrate, or a mixture of at least two thereof.
17. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the ratio of the molar amount of the lithium source to the total molar amount of the metal elements in the manganese-based material in step (1) is (1+ c) to (1-c), wherein 0< c ≦ 0.5.
18. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the calcination in step (1) comprises a first calcination and a second calcination in this order.
19. The method for preparing the lithium-rich manganese-based positive electrode material as claimed in claim 18, wherein the temperature of the first calcination is 350-650 ℃.
20. The method of preparing a lithium-rich manganese-based positive electrode material of claim 18, wherein the time for the first calcination is 2 to 10 hours.
21. The method for preparing the lithium-rich manganese-based positive electrode material as claimed in claim 18, wherein the temperature of the second calcination is 800-1000 ℃.
22. The method of claim 18, wherein the second calcining time is between 2 and 20 hours.
23. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the atmosphere for the calcination in step (1) is an oxygen-containing atmosphere.
24. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the temperature of the heat treatment is 50 to 100 ℃.
25. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the time of the stripping treatment in step (2) is 2 to 10 hours.
26. The method for preparing a lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the rotation speed of the centrifugation in the step (2) is 1000-10000 r/min.
27. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the time for centrifugation in step (2) is 10-60 min.
28. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the suspension of the lithium-rich manganese-based material in step (2) is in a colloidal state.
29. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the concentration of the suspension of the lithium-rich manganese-based material in step (2) is 1 to 10 wt%.
30. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 1, wherein the drying method in step (3) comprises vacuum drying.
31. The method of claim 30, wherein the vacuum drying is performed at a temperature of 50-120 ℃.
32. The method for preparing a lithium-rich manganese-based positive electrode material of claim 30, wherein the vacuum drying time is 10-36 hours.
33. The method of making a lithium-rich manganese-based positive electrode material of claim 1, further comprising stripping the lithium-rich manganese-based positive electrode material from the substrate.
34. The method of preparing a lithium-rich manganese-based positive electrode material of claim 1, comprising the steps of:
(1') preparing a mixed solution containing a nickel source, manganese salt and cobalt salt, then adding a precipitator, reacting at 40-80 ℃, adding a buffer solution to adjust the pH value of the reaction solution to 7-12, and drying to obtain the manganese-based material;
(2 ') mixing the manganese-based material obtained in the step (1') with a lithium source, and calcining to obtain a lithium-rich manganese-based material intermediate;
(3 ') mixing the lithium-rich manganese-based material intermediate obtained in the step (2') with stripping liquid, carrying out stripping treatment, and centrifuging to obtain a suspension of the lithium-rich manganese-based material, wherein the mass ratio of the lithium-rich manganese-based material intermediate to the stripping liquid is (0.01-0.1): 1;
(4 ') coating the suspension obtained in the step (3') on a substrate, and drying the substrate in vacuum at the temperature of between 50 and 120 ℃ for 10 to 36 hours to obtain the lithium-rich manganese-based positive electrode material.
35. Use of the lithium-rich manganese-based positive electrode material prepared by the method for preparing the lithium-rich manganese-based positive electrode material according to any one of claims 1 to 34, wherein the lithium-rich manganese-based positive electrode material is used as a positive electrode material for a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910277165.6A CN109956505B (en) | 2019-04-08 | 2019-04-08 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910277165.6A CN109956505B (en) | 2019-04-08 | 2019-04-08 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| CN109956505A CN109956505A (en) | 2019-07-02 |
| CN109956505A8 CN109956505A8 (en) | 2019-08-20 |
| CN109956505B true CN109956505B (en) | 2021-10-15 |
Family
ID=67025798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910277165.6A Active CN109956505B (en) | 2019-04-08 | 2019-04-08 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109956505B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429254B (en) * | 2019-07-30 | 2020-10-02 | 哈尔滨工业大学（深圳） | Preparation method of lithium ion battery anode material |
| CN111170377B (en) * | 2020-01-19 | 2021-03-09 | 昆明理工大学 | Preparation method of lithium-rich manganese-based positive electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160212A (en) * | 2009-04-07 | 2011-08-17 | 松下电器产业株式会社 | Separator for lithium secondary batteries, and lithium secondary battery using same |
| CN103985853A (en) * | 2013-12-16 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Modification method of lithium-enriched manganese-based solid solution lithium battery cathode material |
| CN106374099A (en) * | 2016-11-02 | 2017-02-01 | 哈尔滨工业大学 | Flexible self-supporting lithium-rich manganese-based cathode for lithium ion battery and preparation method thereof |
| WO2017222895A1 (en) * | 2016-06-23 | 2017-12-28 | Government Of The United States As Represented By The Secretary Of The Air Force | Bendable creasable, and printable batteries with enhanced safety and high temperature stability - methods of fabrication, and methods of using the same |
| CN107706420A (en) * | 2017-11-13 | 2018-02-16 | 山东大学 | A kind of anode material of lithium battery and preparation method thereof |
-
2019
- 2019-04-08 CN CN201910277165.6A patent/CN109956505B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160212A (en) * | 2009-04-07 | 2011-08-17 | 松下电器产业株式会社 | Separator for lithium secondary batteries, and lithium secondary battery using same |
| CN103985853A (en) * | 2013-12-16 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Modification method of lithium-enriched manganese-based solid solution lithium battery cathode material |
| WO2017222895A1 (en) * | 2016-06-23 | 2017-12-28 | Government Of The United States As Represented By The Secretary Of The Air Force | Bendable creasable, and printable batteries with enhanced safety and high temperature stability - methods of fabrication, and methods of using the same |
| CN106374099A (en) * | 2016-11-02 | 2017-02-01 | 哈尔滨工业大学 | Flexible self-supporting lithium-rich manganese-based cathode for lithium ion battery and preparation method thereof |
| CN107706420A (en) * | 2017-11-13 | 2018-02-16 | 山东大学 | A kind of anode material of lithium battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Dual conductive surface engineering of Li-Rich oxides cathode for superior high-energy-density Li-Ion batteries;Fu-Da Yu et al.;《Nano Energy》;20190307;第59卷;第527-536页 * |
| Self-standing Li1.2Mn0.6Ni0.2O2/graphene membrane as a binder-free cathode for Li-ion batteries;Yang Puheng et al.;《RSC Advances》;20181128;第8卷;第39769-39776页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109956505A8 (en) | 2019-08-20 |
| CN109956505A (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106558682B (en) | A kind of the lithium-rich manganese-based of sandwich core-shell structure, spinelle and graphene flexible compound anode and preparation method thereof | |
| CN111525113B (en) | Core-shell structure high-nickel ternary precursor, preparation method thereof and hollow doped high-nickel ternary cathode material | |
| CN106374099A (en) | Flexible self-supporting lithium-rich manganese-based cathode for lithium ion battery and preparation method thereof | |
| CN108428862A (en) | Aluminium cladding ternary mixes zirconium composite material, composite positive pole and its preparation and the application in lithium ion battery | |
| CN109244459B (en) | Codoped flexible sodium-ion battery positive electrode material and preparation method thereof | |
| CN102569773B (en) | Anode material for lithium-ion secondary battery and preparation method thereof | |
| CN103794752A (en) | High voltage nickel lithium manganate cathode materials with core-shell structure and preparation method thereof | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| WO2016176928A1 (en) | Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material | |
| CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
| CN113845158A (en) | Preparation method of porous spherical-structure sodium nickel manganese oxide cathode material | |
| CN113443662B (en) | Preparation method of sodium and/or potassium doped high-nickel ternary positive electrode material | |
| CN111244415A (en) | Air-stable layered transition metal oxide positive electrode material and sodium ion battery thereof | |
| CN108598436A (en) | The positive electrode and preparation method thereof that conducting polymer and manganese dioxide coat altogether | |
| CN107706366A (en) | A kind of positive electrode of indium oxide or tin-doped indium oxide cladding and preparation method thereof | |
| CN109956505B (en) | Lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN106207253B (en) | A kind of aqueous solution lithium ion secondary battery negative pole, electrolyte and battery | |
| CN108878819A (en) | A kind of anode material for lithium-ion batteries and preparation method thereof of the low lithium ion content in surface | |
| CN111490241A (en) | Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN109860536A (en) | A kind of lithium-rich manganese base material and its preparation method and application | |
| CN111342008A (en) | Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof | |
| CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
| CN112687875B (en) | Preparation method and application of nickel molybdate flexible film composite material | |
| CN110197902B (en) | Porous structure open walnut shell-shaped sodium ion battery positive electrode material and preparation method thereof | |
| CN109599553A (en) | A kind of hollow sphere nickel sodium manganate and preparation method thereof, sodium-ion battery positive plate and sodium-ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CI02 | Correction of invention patent application |
Correction item: First applicant Correct: Zhongke (Ma'anshan) New Material Science Park Co., Ltd. False: Zhongke (Ma'anshan) New Material Science Park Co., Ltd. Number: 27-01 Page: The title page Volume: 35 Correction item: First applicant Correct: Zhongke (Ma'anshan) New Material Science Park Co., Ltd. Volume: 35 |
|
| CI02 | Correction of invention patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tan Qiangqiang Inventor after: Ji Xueqian Inventor after: Feng Hailan Inventor before: Tan Qiangqiang Inventor before: Feng Hailan Inventor before: Ji Xueqian |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210827 Address after: 100190 No. two, No. 1, North Haidian District, Beijing, Zhongguancun Applicant after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 243000 2, 1669 north section of Huo Li Shan Road, Ma'anshan high tech Zone, Anhui Applicant before: Zhongke (Ma'anshan) New Material Science Park Co.,Ltd. Applicant before: Institute of Process Engineering, Chinese Academy of Sciences |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |