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CN115224262A - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

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Publication number
CN115224262A
CN115224262A CN202211003639.6A CN202211003639A CN115224262A CN 115224262 A CN115224262 A CN 115224262A CN 202211003639 A CN202211003639 A CN 202211003639A CN 115224262 A CN115224262 A CN 115224262A
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ion battery
lithium ion
lithium
manganese
source
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Inventor
余海军
谢英豪
李爱霞
张学梅
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202211003639.6A priority Critical patent/CN115224262A/en
Publication of CN115224262A publication Critical patent/CN115224262A/en
Priority to PCT/CN2023/077442 priority patent/WO2024036906A1/en
Priority to FR2307979A priority patent/FR3138969A1/en
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium ion battery anode material and a preparation method thereof, belonging to the field of battery materials. The preparation method comprises the following steps: (1) Preparing a solution A from manganese sulfate monohydrate and polyvinylpyrrolidone by using water, adding a potassium ferricyanide solution into the solution A in a titration mode, stirring for reaction, aging after the reaction is completed, filtering, and washing to obtain manganese ferricyanide; (2) Uniformly dispersing manganese hexacyanoferrate, a nickel source, a lithium source, polyimide and an anionic surfactant with water, carrying out ball milling treatment, and then carrying out heat preservation for 15-20 h at the temperature of 750-950 ℃ to obtain the lithium ion battery cathode material. The material has a multilayer sheet structure, is beneficial to fully contacting with electrolyte, and can also effectively relieve stress caused by volume change of the anode material in the charging and discharging processes; in addition, the iron phase in the material can be stabilized in an oxide ion frame and keep a higher valence state, and the charge and discharge capacity can be higher by matching with the nitrogen-containing coated carbon layer.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention relates to the field of battery materials, in particular to a lithium ion battery anode material and a preparation method thereof.
Background
Lithium cobaltate is the earliest commercialized lithium ion battery anode material, has higher capacity density and service performance, but because cobalt element has high toxicity and less resource content, in order to reduce the cost of the material, the doping modification of lithium cobaltate is carried out by nickel and manganese elements to reduce the relative content of the cobalt element, and meanwhile, three metal elements can generate synergistic effect, and the prepared ternary material can also generate good electrochemical performance.
With the gradual and deep research of people, people begin to adopt iron element to completely replace cobalt element in ternary materials, and the prepared Li-Fe-Ni-Mn-O material has the performance comparable to that of commercial ternary materials, and meanwhile, the production cost is lower and the safety is higher. However, the introduction of the iron element directly causes the appearance of the ternary material to be changed, and a good layered structure cannot be maintained, so that the electrochemical stability of the ternary material in the using process cannot be guaranteed; meanwhile, the iron element has certain instability, and impurities are easy to appear in the process of preparing the product, so that the product performance is influenced.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a preparation method of a lithium ion battery anode Li-Fe-Ni-Mn-O composite material with a layered structure, the preparation method takes manganese hexacyanoferrate with a special shape as a basic structure, and introduces cross-linked nitrogen-containing polymer polyimide and a specific surfactant for mixing precursors, and the Li-Fe-Ni-Mn-O composite material with a multilayer sheet structure can be effectively obtained by a high-temperature solid phase method, the synthesis path of the material is simple, the multilayer sheet structure is beneficial to full contact of electrolyte, and the stress caused by volume change of the anode material in the charge and discharge process can be effectively relieved; in addition, through the stable doping of the nickel phase and the manganese phase, the iron phase in the material can be effectively stabilized in an oxide ion frame and keeps a higher valence state, and the charge and discharge capacity can be higher by matching with the nitrogen-containing coated carbon layer with high conductivity. In order to achieve the purpose, the invention adopts the technical scheme that:
in order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a lithium ion battery anode material comprises the following steps:
(1) Preparing a solution A from manganese sulfate monohydrate and polyvinylpyrrolidone by using water, adding a potassium ferricyanide solution into the solution A in a titration mode, stirring for reaction, aging after the reaction is completed, filtering, and washing to obtain manganese ferricyanide;
(2) Uniformly dispersing manganese ferricyanide, a nickel source, a lithium source, polyimide and an anionic surfactant with water, performing ball milling treatment, and then performing heat preservation at 750-950 ℃ for 15-20 h to obtain the lithium ion battery cathode material.
According to the preparation method of the lithium ion battery cathode material, the manganese hexacyanoferrate obtained by the method is used as an iron source and a manganese source, and has a special cubic nano structure, and meanwhile, the structure is hollow inside, so that when the manganese hexacyanoferrate is in contact reaction with a nickel source and a lithium source, the reaction diffusion degree of lithium ions can be effectively improved, and finally when a Li-Fe-Ni-Mn-O composite material is sintered and synthesized, the cubic hollow nano structure collapses due to stress and is gradually converted into fragments with multiple layer sheet structure layers, so that the area of a product in contact with electrolyte is effectively improved, and the volume change stress of the material in charging and discharging is relieved; in addition, the iron phase in the existing iron-doped Li-Fe-Ni-Mn-O or Li-Fe-Co-Ni-Mn-O material is difficult to maintain a higher valence state, but an iron source is introduced in the technical scheme of the invention in the form of ferricyanide, the iron phase can be effectively kept in an oxide ion frame through the collocation of manganese and nickel element in the raw material, and the charge-discharge capacity of the whole material is effectively improved.
On the other hand, because a lithium source is generally introduced into a precursor by a ball milling method in the process of synthesizing a ternary material or a Li-Fe-Ni-Mn-O material by a traditional solid phase method, the method is easy to operate, but poor in mixture uniformity and causes more raw material loss. The existing solution is mostly to introduce an organic solvent and some surfactants as dispersants to relieve particle agglomeration, but for components dissolved in the solvent, the components are lost along with the volatilization or loss of the solvent, and for insoluble components, the components still gradually stay at the bottom of a reaction vessel in the ball milling process, and the dispersion degree is improved to a limited extent, so that the preparation method of the product adopts polyimide as a medium, under the condition that water is used as a disperse phase, the polyimide can effectively cross-link or wrap each Li-Fe-Ni-Mn-O ternary positive electrode material precursor, and keeps good dispersion under the action of a hydrophobic group generated by an anionic surfactant (since the anionic surfactant easily generates a hydrophobic group in water, for water-soluble polyimide, the precursor sources can be effectively cross-linked when the water-soluble polyimide is dissolved in water, and for oil-soluble polyimide, under the action of the hydrophobic group, the polyimide can also stably disperse in a molecular form in water and wrap each precursor source, and both action modes can effectively improve the dispersion of the precursor sources when the precursors are mixed and sintered at high temperature, and the polyimide plays a role of protecting a conductive material and also can effectively improve the whole conductive carbon layer.
Preferably, the ratio of the mole of the manganese sulfate monohydrate to the mass of the polyvinylpyrrolidone in the solution A is (0.0025-0.0035) mol: (1-5) g, wherein the concentration of the solution A is 10-15 g/L.
Preferably, the concentration of the potassium ferricyanide solution is 5-10 g/L.
Preferably, the molar ratio of the sum of iron element and manganese element in the manganese hexacyanoferrate to the nickel element in the nickel source is n (Mn + Fe): n (Ni) = (9).
Preferably, the molar ratio of the manganese hexacyanoferrate to the iron element in the nickel source to the lithium element in the lithium source is: n (Mn + Fe + Ni): n (Li) =1 (1 to 1.05).
The Li-Fe-Ni-Mn-O composite material prepared by the raw material proportion has higher content of manganese element, and can effectively improve the discharge capacity and the cycle stability of the whole material.
Preferably, the nickel source is at least one of nickel acetate and nickel carbonate; the lithium source is at least one of lithium acetate and lithium carbonate.
Preferably, the anionic surfactant is at least one of carboxylate anionic surfactant and sulfonate anionic surfactant.
Preferably, the mass ratio of manganese ferricyanide, nickel source, lithium source, polyimide and anionic surfactant is: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1: (0.4-0.6): (0.4-0.6).
The proper amount of the polyimide and the anionic surfactant can effectively improve the dispersibility and uniformity of the raw materials in the dispersing process, and meanwhile, the raw materials can not be completely separated from a water body system to cause the adhesion to a grinding wall.
The invention also aims to provide the lithium ion battery cathode material prepared by the preparation method of the lithium ion battery cathode material.
The Li-Fe-Ni-Mn-O composite material for the lithium ion battery anode material prepared by the method disclosed by the invention is an ideal multilayer laminated structure constructed by special raw material selection and synthesis processes, so that the stability of the product in the process of lithium ion de-intercalation is effectively guaranteed, and meanwhile, because an iron source is introduced in the form of ferrimanganic cyanide and a N-containing polymer is adopted as an auxiliary processing reagent, the stability of an iron phase in the obtained material is higher, the purity of the whole material is higher, and meanwhile, the conductivity of the whole material is also obviously improved due to the introduction of nitrogen.
The invention also aims to provide a lithium ion battery positive pole piece which is prepared from the lithium ion battery positive pole material.
The preparation method has the beneficial effects that manganese hexacyanoferrate with a special shape is used as a basic structure, cross-linked nitrogen-containing polymer polyimide and a specific anionic surfactant are introduced to mix a precursor, and a Li-Fe-Ni-Mn-O composite material with a multilayer sheet structure can be effectively obtained by a high-temperature solid phase method, has the multilayer sheet structure, is beneficial to fully contacting with electrolyte, and can also effectively relieve stress caused by volume change of the positive electrode material in the charging and discharging process; in addition, the iron phase in the material can be effectively stabilized in an oxide ion frame and keeps a higher valence state, and the charge and discharge capacity can be higher by matching with the nitrogen-containing coated carbon layer with high conductivity.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents, raw materials and instruments designed in the practice of the invention and the comparative examples are common reagents, raw materials and instruments unless otherwise specified.
Example 1
One embodiment of the lithium ion battery anode material and the preparation method thereof comprises the following steps:
(1) Preparing 12g/L solution A from 0.003mol of manganese sulfate monohydrate and 3g of polyvinylpyrrolidone by using water and a small amount of ethanol, adding 12g/L potassium ferricyanide solution into the solution A in a titration form, stirring for reaction until the turbidity of the solution is not changed, aging at normal temperature for 24 hours after the reaction is completed, filtering, washing with water and ethanol respectively, and drying to obtain manganese ferricyanide;
(2) Putting manganese hexacyanoferrate, nickel acetate, lithium acetate, polyimide and an anionic surfactant dodecyl glycidyl ether DEG (Senfinada chemical industry) into a ball milling tank, adding 5 times of water by mass, uniformly dispersing, performing ball milling treatment for 24 hours at the speed of 200rpm by using a planetary ball mill, drying the obtained mixed slurry at normal temperature for 24 hours, and then putting the dried mixed slurry into an air atmosphere to perform heat preservation for 18 hours at 850 ℃ to obtain the lithium ion battery anode material; wherein each component is mixedTheoretical reaction product of metal elements in alloy material is combined with formula Li (Mn) 0.48 Fe 0.32 Ni 0.2 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8; the mass ratio of manganese hexacyanoferrate to nickel source to lithium source to polyimide to anionic surfactant is as follows: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1g:0.5g:0.5g.
Example 2
The difference between this example and example 1 is only that the theoretical reaction product of the metal elements in the respective mixtures is Li (Mn) 0.51 Fe 0.34 Ni 0.15 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8.5.
Example 3
The difference between this example and example 1 is only that the theoretical reaction product of the metal elements in the respective mixtures is Li (Mn) 0.54 Fe 0.36 Ni 0.1 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) =9.
Example 4
The difference between this example and example 1 is only that the theoretical reaction product of the metal elements in the respective mixtures is Li (Mn) 0.57 Fe 0.38 Ni 0.05 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 9.5.
Example 5
The difference between this example and example 1 is only that the mass ratio of manganese ferricyanide, nickel source, lithium source, polyimide and anionic surfactant is: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1g:0.6g:0.6g.
Example 6
The difference between this example and example 1 is only that the mass ratio of manganese ferricyanide, nickel source, lithium source, polyimide and anionic surfactant is: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1g:0.8g:0.8g.
Comparative example 1
A lithium ion battery anode material and a preparation method thereof comprise the following steps:
placing iron acetate, manganese acetate, nickel acetate, lithium acetate, polyimide and anionic surfactant dodecyl glycerol ether in a ball milling tank, adding 5 times of water by mass, uniformly dispersing, carrying out ball milling treatment for 24 hours at the speed of 200rpm by using a planetary ball mill, drying the obtained mixed slurry at normal temperature for 24 hours, and placing the dried mixed slurry in an air atmosphere to keep the temperature at 850 ℃ for 18 hours to obtain the lithium ion battery anode material; wherein the reaction product of the metal elements in each mixture according to theory is combined with Li (Mn) 0.48 Fe 0.32 Ni 0.2 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8; the mass ratio of the iron source, the manganese source, the nickel source, the lithium source, the polyimide and the anionic surfactant is as follows: m (iron source + manganese source + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1g:0.5g:0.5g.
Comparative example 2
A lithium ion battery anode material and a preparation method thereof comprise the following steps:
(1) Preparing a solution A with the concentration of 12g/L by 0.003mol of manganese sulfate monohydrate and 3g of polyvinylpyrrolidone through water and a small amount of ethanol, adding a 12g/L potassium ferricyanide solution into the solution A in a titration mode, stirring for reaction until the turbidity of the solution is not changed, aging at normal temperature for 24 hours after the reaction is completed, filtering, washing with water and ethanol respectively, and drying to obtain manganese ferricyanide;
(2) Putting manganese hexacyanoferrate, nickel acetate, lithium acetate and polyimide into a ball milling tank, adding 5 times of mass of the mixture to disperse the mixture uniformly, performing ball milling treatment for 24 hours by adopting a planetary ball mill at the speed of 200rpm, drying the obtained mixed slurry at normal temperature for 24 hours, and then putting the dried mixed slurry into an air atmosphere to perform heat preservation at 850 ℃ for 18 hours to obtain the lithium ion battery anode material; wherein the reaction product of the metal elements in each mixture according to theory is combined with Li (Mn) 0.48 Fe 0.32 Ni 0.2 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8; sources of manganese and nickel ferricyanideThe mass ratio of the lithium source to the polyimide is as follows: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide) =1g:0.5g.
Comparative example 3
A lithium ion battery anode material and a preparation method thereof comprise the following steps:
(1) Preparing a solution A with the concentration of 12g/L by 0.003mol of manganese sulfate monohydrate and 3g of polyvinylpyrrolidone through water and a small amount of ethanol, adding a 12g/L potassium ferricyanide solution into the solution A in a titration mode, stirring for reaction until the turbidity of the solution is not changed, aging at normal temperature for 24 hours after the reaction is completed, filtering, washing with water and ethanol respectively, and drying to obtain manganese ferricyanide;
(2) Putting manganese hexacyanoferrate, nickel acetate, lithium acetate and anionic surfactant dodecyl glycidyl ether into a ball milling tank, adding 5 times of water by mass, uniformly dispersing, carrying out ball milling treatment for 24 hours at the speed of 200rpm by adopting a planetary ball mill, drying the obtained mixed slurry at normal temperature for 24 hours, and then putting the dried mixed slurry into an air atmosphere to keep the temperature at 850 ℃ for 18 hours to obtain the lithium ion battery anode material; wherein the reaction product of the metal elements in each mixture according to theory is combined with Li (Mn) 0.48 Fe 0.32 Ni 0.2 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8; the mass ratio of manganese hexacyanoferrate to nickel source to lithium source to anionic surfactant is as follows: m (manganese hexacyanoferrate + nickel source + lithium source): m (anionic surfactant) =1g:0.5g.
Comparative example 4
One embodiment of the lithium ion battery anode material and the preparation method thereof comprises the following steps:
(1) Preparing a solution A with the concentration of 12g/L by 0.003mol of manganese sulfate monohydrate and 3g of polyvinylpyrrolidone through water and a small amount of ethanol, adding a 12g/L potassium ferricyanide solution into the solution A in a titration mode, stirring for reaction until the turbidity of the solution is not changed, aging at normal temperature for 24 hours after the reaction is completed, filtering, washing with water and ethanol respectively, and drying to obtain manganese ferricyanide;
(2) Manganese hexacyanoferrate, nickel acetate, lithium acetate, polyimide and nonionic surfactant AEO-9 (Daihang chemical)Placing the mixture in a ball milling tank, adding 5 times of water by mass, uniformly dispersing, performing ball milling treatment for 24 hours at the speed of 200rpm by using a planetary ball mill, drying the obtained mixed slurry at normal temperature for 24 hours, and then placing the dried mixed slurry in an air atmosphere to perform heat preservation for 18 hours at 850 ℃ to obtain the lithium ion battery anode material; wherein the reaction product of the metal elements in each mixture according to theory is combined with Li (Mn) 0.48 Fe 0.32 Ni 0.2 )O 2 Calculating the element ratio as n (Mn + Fe + Ni): n (Li) =1, n (Mn + Fe): n (Ni) = 8; the mass ratio of manganese ferricyanide, a nickel source, a lithium source, polyimide and a nonionic surfactant is as follows: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (nonionic surfactant) =1g:0.5g:0.5g.
Effect example 1
In order to verify the electrochemical performance of the lithium ion battery positive electrode material, the materials of the embodiments and the comparative examples are mixed with conductive carbon black and PVDF according to the mass ratio of 8.
TABLE 1
Figure BDA0003806243330000081
Figure BDA0003806243330000091
As can be seen from Table 1, the initial discharge specific capacity of the product obtained in each example is higher at low rate, and can reach more than 155mAh/g, and the capacity retention rate after 100 times of circulation is also more than 80%, and when the product is subjected to high rate circulation and returns to low rate circulation again, the discharge specific capacity of the product is still considerable, and can reach 145mAh/g at most. From examples 1 to 4, it can be seen that the cycle stability of the product is improved to some extent with the decrease of the nickel element content, but the discharge capacity is decreased to some extent, and based on the comprehensive properties, the ratio of n (Mn + Fe): and n (Ni) is 9. It can be seen from comparison between the product performances of example 1, example 5 and example 6 that, as the addition amounts of the polyimide and the surfactant are increased too much, the dispersibility of each precursor of the product is better, and the doping content of the nitrogen element is also higher, but relatively, the precursors may be completely separated from the water phase in the mixing process, the degree of uniform mixing is rather lower, and the cycle performance and rate capability of the product are also affected. In contrast, the product of comparative example 1 was prepared from common starting materials, and although surfactant and polyimide were also introduced at last, the overall effect was poor, the cycle performance of the product was poor, the initial capacity was low and the rate performance was poor. Comparative examples 2 and 3, in which no surfactant and polyimide were introduced during the grinding and mixing of the precursor, have significantly deteriorated cycle performance and rate performance compared to the product of example 1, while the initial specific discharge capacity of the product of comparative example 3 is lower, which indicates that the doping loss of nitrogen also affects the initial capacity of the product. The product of comparative example 4 is different from the product of example 1 in the preparation process only by using different types of surfactants, and obviously has the performance equivalent to that of the product of comparative example 2 without introducing the surfactant, which indicates that the nonionic surfactant can not effectively help the precursor materials to be uniformly mixed and dispersed, and the auxiliary agent is not suitable for the preparation process system of the product of the invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
(1) Preparing a solution A by using water for manganese sulfate monohydrate and polyvinylpyrrolidone, adding a potassium ferricyanide solution into the solution A in a titration form, stirring for reaction, aging after the reaction is completed, filtering, and washing to obtain manganese ferricyanide;
(2) Uniformly dispersing manganese ferricyanide, a nickel source, a lithium source, polyimide and an anionic surfactant with water, performing ball milling treatment, and then performing heat preservation at 750-950 ℃ for 15-20 h to obtain the lithium ion battery cathode material.
2. The method for preparing the positive electrode material of the lithium ion battery according to claim 1, wherein the ratio of the moles of the manganese sulfate monohydrate to the mass of the polyvinylpyrrolidone in the solution a is (0.0025-0.0035) mol: (1-5) g, wherein the concentration of the solution A is 10-15 g/L.
3. The method for preparing the positive electrode material of the lithium ion battery according to claim 1, wherein the concentration of the potassium ferricyanide solution is 5 to 10g/L.
4. The method for preparing the positive electrode material of the lithium ion battery according to claim 1, wherein the molar ratio of the sum of iron and manganese in the manganese hexacyanoferrate to nickel in the nickel source is n (Mn + Fe): n (Ni) = (9).
5. The method for preparing the lithium ion battery cathode material according to claim 1, wherein the molar ratio of manganese hexacyanoferrate, iron element in the nickel source, iron element, nickel element and lithium element in the lithium source is: n (Mn + Fe + Ni): n (Li) =1 (1 to 1.05).
6. The method for preparing the lithium ion battery cathode material according to claim 1, wherein the nickel source is at least one of nickel acetate and nickel carbonate; the lithium source is at least one of lithium acetate and lithium carbonate.
7. The method for preparing a positive electrode material of a lithium ion battery according to claim 1, wherein the anionic surfactant is at least one of carboxylate anionic surfactant and sulfonate anionic surfactant.
8. The method for preparing the positive electrode material of the lithium ion battery according to claim 1, wherein the mass ratio of manganese ferricyanide, a nickel source, a lithium source, polyimide and an anionic surfactant is as follows: m (manganese hexacyanoferrate + nickel source + lithium source): m (polyimide): m (anionic surfactant) =1: (0.4-0.6): (0.4-0.6).
9. The lithium ion battery cathode material prepared by the method for preparing the lithium ion battery cathode material according to any one of claims 1 to 8.
10. A positive pole piece of a lithium ion battery is characterized in that the positive pole piece is prepared from the positive pole material of the lithium ion battery in claim 9.
CN202211003639.6A 2022-08-19 2022-08-19 Lithium ion battery anode material and preparation method thereof Pending CN115224262A (en)

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CN114883523B (en) * 2022-05-16 2023-09-22 电子科技大学长三角研究院(湖州) Positive electrode material, preparation method thereof and application of positive electrode material in sodium ion battery
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