CN111600013A - Manganese source precursor, manganese-based lithium battery positive electrode material and preparation method thereof - Google Patents

Manganese source precursor, manganese-based lithium battery positive electrode material and preparation method thereof Download PDF

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CN111600013A
CN111600013A CN202010396248.XA CN202010396248A CN111600013A CN 111600013 A CN111600013 A CN 111600013A CN 202010396248 A CN202010396248 A CN 202010396248A CN 111600013 A CN111600013 A CN 111600013A
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manganese
lithium battery
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毕亚凡
刘璐
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Wuhan Institute of Technology
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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
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • C01G45/00—Compounds of manganese
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    • H—ELECTRICITY
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    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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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Abstract

The invention provides a manganese source precursor, a manganese-based lithium battery anode material and a preparation method thereof, wherein the manganese source precursor for the manganese-based lithium battery anode material is MnO2Sequentially carrying out deoxidation roasting and disproportionation reaction of hot sulfuric acid solution to obtain active MnO2And (4) crystal grains. The invention is realized by adding commercially available MnO2Active MnO prepared by roasting and disproportionation2The crystal grain is used as a high-valence state manganese source precursor for synthesizing the positive electrode material of the manganese-based lithium battery and is prepared by controlling the distribution ratio of the manganese source precursor to each synthetic element, the calcination temperature, the calcination time and other factorsThe manganese-based lithium ion battery anode materials with different crystal structures and different electrochemical properties are prepared, and the obtained manganese-based lithium ion battery anode material is ensured to have a preset crystal structure, so that excellent charge-discharge specific capacity, rate capability and cycling stability are realized.

Description

Manganese source precursor, manganese-based lithium battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of battery electrode materials, in particular to a manganese source precursor, a manganese-based lithium battery anode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high voltage, long cycle life, large specific energy and the like, is widely applied to various industrial and living fields, and is one of the most promising power sources at present. However, the energy density and the cycling stability of the existing commercial lithium ion battery still cannot meet the requirements of power equipment such as unmanned aerial vehicles and electric vehicles and high-capacity energy storage batteries which are developed increasingly. Since the positive electrode of the lithium battery is a key factor determining the energy density and electrochemical performance of the lithium battery, further development of positive electrode materials of various types of lithium batteries with large capacity is required.
At present, in order to obtain higher capacity and control the production cost of the lithium battery cathode material, the research and development of the manganese-based lithium battery cathode material with higher manganese element content draws more and more attention, and particularly, the lithium-rich manganese-based cathode material has higher electric capacity and is regarded as the material of the next generation lithium ion battery cathode. Common preparation methods of manganese-based lithium battery cathode materials include a sol-gel method, a spray drying method, a coprecipitation method, a hydrothermal method and the like, but the synthesis process still faces the problems of complex process, high preparation cost, great industrialization difficulty and the like, and particularly, in the selection of a manganese source, most of the manganese-based lithium battery cathode materials adopt soluble low-valence manganese salt (Mn)2+). Due to the characteristic that the high-valence manganese oxide is easy to generate a deoxidation reaction in the high-temperature calcination process and is reduced into low-valence manganese, the low-valence manganese source is difficult to completely form a valence state and a crystal form preset by the anode material in the high-temperature sintering process, so that the manganese-based anode material prepared by the method is difficult to ensure to have a required stable crystal form structure and electrochemical performance. In addition, the industry mostly adopts a coprecipitation method to produce the ternary precursor at present, and the production process has the problems of a large amount of salt-containing wastewater, high production cost and the like. Therefore, the selection of a proper manganese source material is very important for preparing the positive electrode material of the manganese-based lithium battery with complete crystal structure and excellent electrochemical performance.
Disclosure of Invention
In view of the above, the present invention is directed to provide a manganese source precursor for preparing a positive electrode material of a manganese-based lithium battery, so as to solve the problems of poor crystal structure, poor electrochemical performance stability, high production cost, and the like of the existing positive electrode material of the manganese-based lithium battery due to the selection of a low-valence manganese source.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
manganese-based lithiumThe manganese source precursor for the battery anode material is MnO2Sequentially carrying out deoxidation roasting and disproportionation reaction of hot sulfuric acid solution to obtain active MnO2And (4) crystal grains.
Optionally, the MnO2Is one or more of electrolytic manganese dioxide, chemical manganese dioxide and purified electrolytic manganese anode mud.
A second object of the present invention is to provide a method for preparing the manganese source precursor for a positive electrode material of a manganese-based lithium battery, the method comprising the steps of:
1) deoxidizing and roasting: MnO of2Roasting for 3-10 h under the conditions of natural atmosphere and temperature of 570-850 ℃, and naturally cooling to normal temperature to obtain Mn2O3；
2) Disproportionation reaction treatment of hot sulfuric acid solution: mixing the Mn with a solid-liquid ratio of 1: 4-82O3Adding the precursor into a sulfuric acid solution for disproportionation, and after the disproportionation is finished, filtering, washing and drying to obtain active MnO as a manganese source precursor2And (4) crystal grains.
Optionally, the mass concentration of the sulfuric acid solution in the step 2) is 10-50%; the disproportionation temperature of the disproportionation treatment in the step 2) is 50-100 ℃, and the disproportionation reaction time is 0.5-4 h.
The third purpose of the invention is to provide a manganese-based lithium battery anode material, which is prepared by blending the manganese source precursor and preset synthetic elements according to a certain component proportion, then carrying out impregnation, evaporation dehydration, drying and calcination, wherein the preset synthetic elements comprise Li and one or more of Ni, Co, Fe, Cr, Al, La and Ce; or the manganese source precursor and preset synthetic elements are mixed according to a certain component proportion, then a multi-element precursor is prepared by adopting an impregnation method or a coprecipitation method, and the multi-element precursor is mixed with a lithium source and then calcined to obtain the lithium ion battery, wherein the preset synthetic elements comprise one or more of Ni, Co, Fe, Cr, Al, La and Ce.
Optionally, the positive electrode material of the manganese-based lithium battery is a layered lithium-rich positive electrode material or is not a layered lithium-rich positive electrode materialA lithium-rich positive electrode material; the chemical formula of the layered lithium-rich cathode material is (1-x) Li2MnO3·xLiMO2Wherein x is more than or equal to 0 and less than or equal to 1.0, and M is one or more of Ni, Co, Mn, Fe, Cr, La, Ce and Al; the chemical formula of the non-lithium-rich cathode material is LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5, and M is one or more of Ni, Co, Fe, La, Ce, Al and Cr.
Optionally, the preset synthesis element Li is derived from one or more of lithium nitrate, lithium carbonate and lithium hydroxide; the preset synthetic element Ni is derived from one or more of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel carbonate and nickel oxalate; the preset synthetic element Co is derived from one or more of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt oxalate and cobalt acetate; the preset synthetic element Fe is derived from one or more of ferric nitrate, ferric sulfate, ferric chloride, ferric acetate and ferric oxalate; the preset synthetic element Cr is from one of chromium nitrate, chromium sulfate and chromium chloride; the preset synthetic element Al is derived from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the preset synthesis element La is derived from one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate; the preset synthetic element Ce is derived from one or more of cerium nitrate, cerium acetate, cerium carbonate and cerium chloride.
The fourth objective of the present invention is to provide a method for preparing the manganese-based lithium battery anode material, wherein the preparation method comprises the steps of blending the manganese source precursor and a predetermined synthetic element according to a certain component ratio, impregnating, evaporating, dehydrating, drying, and calcining to obtain the manganese-based lithium battery anode material, wherein the preparation method specifically comprises the following steps:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, soaking for 0.5-12 h at 60-120 ℃, evaporating, dehydrating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery anode material.
The fifth objective of the present invention is to provide a method for preparing the manganese-based lithium battery cathode material, the preparation method comprises the steps of preparing the manganese source precursor and preset synthesis elements according to a certain component ratio, preparing a multi-element precursor by an impregnation method, mixing the multi-element precursor with a lithium source, and calcining the mixture to obtain the manganese-based lithium battery cathode material, wherein the preparation method specifically comprises the following steps:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, preserving heat and impregnating for 0.5-12 h at the temperature of 60-120 ℃, evaporating, dehydrating, drying, decomposing and roasting for 1-8 h at the temperature of 125-280 ℃, cooling, and grinding to obtain a multi-element precursor;
adding a lithium source into the multi-element precursor, soaking for 3-10 h at 100-250 ℃, evaporating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery cathode material.
The sixth object of the present invention is to provide a method for preparing the manganese-based lithium battery positive electrode material, wherein the preparation method comprises the steps of blending the manganese source precursor and preset synthesis elements according to a certain component ratio, preparing a multi-element precursor by a coprecipitation method, mixing the multi-element precursor with a lithium source, and calcining the mixture to obtain the manganese-based lithium battery positive electrode material, wherein the preparation method specifically comprises the following steps:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, adding a potassium hydroxide or sodium hydroxide solution under the stirring condition, adjusting the pH of the solution to 7 to less than pH 11, carrying out coprecipitation reaction, and after the coprecipitation reaction is finished, filtering, washing and drying to obtain a multi-element precursor;
adding a lithium source into the multi-element precursor, soaking for 3-10 h at 100-250 ℃, evaporating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery cathode material.
Optionally, the concentration of the soluble salt solution containing the preset synthetic elements is 1.0-3.5 mol.L-1(ii) a The concentration of the potassium hydroxide or the sodium hydroxide solution is 1.0-4.0mol·L-1。
Compared with the prior art, the manganese source precursor for the manganese-based lithium battery cathode material has the following advantages:
1. the invention is realized by adding commercially available ordinary MnO2Performing high-temperature deoxidation roasting to generate Mn with a three-dimensional network structure2O3After the crystal particles are subjected to disproportionation treatment by a hot acid solution to obtain MnO2Grains of a network structure, the MnO2Chemical etching and lattice reforming are carried out on crystal grains, and a plurality of nano-sized pits and columns are formed on the surfaces of the crystal grains, so that the crystal grains have extremely large specific surface area, provide contact reaction opportunities and structural space for doping other cations or anions, and simultaneously improve Gibbs free energy of the crystal grains, thereby belonging to active MnO2And (4) crystal grains. When the precursor is used for preparing the positive electrode material of the manganese-based lithium battery, the obtained positive electrode material of the manganese-based lithium battery can be ensured to have the preset manganese valence state and crystal structure, so that the excellent charge-discharge capacity, rate capability and cycling stability of the positive electrode material of the manganese-based lithium battery are realized.
2. The manganese-based lithium ion battery anode materials with different crystal structures and different electrochemical properties can be prepared by controlling the distribution ratio of the manganese source precursor to each synthetic element, the calcination temperature, the calcination time and other factors, and various types of manganese-based lithium ion battery anode materials with high capacity, excellent charge-discharge rate performance and cycle stability are developed on the basis of the manganese source precursor, so that the application range is wide.
3. The invention has the characteristics of simple preparation process, mild production control conditions, low production cost, less generation of three wastes such as waste water, waste salt and the like, and is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows MnO in the present invention2By roastingMn obtained after treatment2O3SEM images of the crystal particles;
FIG. 2 shows MnO in the present invention2Active MnO obtained after roasting and disproportionation2SEM image of crystal particles.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Common Electrolytic Manganese Dioxide (EMD) and Chemical Manganese Dioxide (CMD) are common electrode materials for disposable chemical batteries, and are difficult to be directly used as manganese sources for synthesizing positive electrode materials of lithium batteries due to the problems of the structure, chemical activity or purity and the like. However, EMD or high-purity CMD is roasted at 550-850 ℃ for deoxidation and then converted into Mn2O3Wherein Mn-O is broken, and the crystal structure is also changed to form a net crystal structure. If Mn after deoxidation is to be calcined2O3Then the mixture is treated by hot sulfuric acid, namely disproportionation reaction is carried out to generate equimolar MnSO4And MnO2The specific reaction formula is as follows.
4MnO2＝2Mn2O3+O2
Mn2O3+H2SO4＝MnSO4+MnO2+H2O
MnO obtained after disproportionation2Is an active micro-grain formed by chemical etching and lattice reforming. The crystal grain not only retains the original matrix (Mn)2O3) The surface of the reticular crystal structure frame is etched by acid to form a plurality of nanometer-sized recesses and stabs, thereby forming a great specific surface area and providing contact reaction opportunities and structural spaces for the doping of other cations or anions. Meanwhile, during the disproportionation process, a plurality of vacancies and defects are formed due to low-temperature disproportionation and rearrangement in the crystal lattice, so that the overall energy state and the active site density of the crystal material are improved, and the MnO obtained after the disproportionation is2The net crystal grain has stronger chemical activity and belongs to active MnO2Crystal grains capable of being used for preparing manganese-based lithium ion battery positive electrodeThe high-valence manganese source precursor of the cathode material ensures that the prepared manganese-based cathode material has a preset crystal structure, thereby realizing excellent charge and discharge capacity, rate capability and cycling stability.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A preparation method of a manganese-based lithium battery positive electrode material specifically comprises the following steps:
1) deoxidizing and roasting: adding a predetermined amount of manganese dioxide (MnO)2) Feeding into rotary kiln, roasting at 750 + -50 deg.C in natural atmosphere for 5 hr, naturally cooling to room temperature to obtain Mn2O3Wherein, MnO is2Is a commercial manganese dioxide, in particular to an electrolytic manganese dioxide, the particle size of which is in the range of-100 to-50 meshes;
2) disproportionation reaction treatment of hot sulfuric acid solution: the obtained Mn is measured according to the solid-to-liquid ratio of 1: 52O3Then adding the manganese oxide into a sulfuric acid solution with the mass concentration of 20% for disproportionation, wherein the disproportionation temperature of the disproportionation is 70 ℃, the disproportionation time is 1.5 hours, the disproportionation rate is more than 98% after the disproportionation is finished, and then filtering, washing, drying and weighing are carried out to obtain the active MnO serving as the manganese source precursor2Crystal grains are reserved;
3) adding the manganese source precursor into a container containing a certain amount of mixed saturated solution of nickel nitrate and cobalt nitrate according to a pre-designed ratio of Li, Mn, Ni and Co of 1.0: 1.5: 0.45: 0.05, heating and keeping the temperature at 90 ℃, soaking for 8 hours at the constant temperature, directly evaporating, dehydrating and drying, then putting the obtained powder into a muffle furnace and roasting for 4 hours at the temperature of 250 ℃, cooling and grinding to obtain a multi-element precursor, namely a manganese nickel cobalt oxide precursor, wherein no wastewater is generated in the process;
4) adding heat saturated lithium hydroxide solution into the prepared manganese cobalt oxide precursor according to the preset mixture ratio of Li, Mn, Ni and Co of 1.0: 1.5: 0.45: 0.05, preserving the heat of the obtained manganese cobalt oxide precursor in a sealed reactor for 8 hours at the temperature of 150 ℃, impregnating, evaporating, drying and grindingThen placing the mixture in a tunnel kiln, calcining the mixture for 8 hours at the temperature of 800 +/-50 ℃, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the manganese-based lithium battery anode material, namely the spinel-structured ternary composite lithium manganate anode material (LiMn)1.5Ni0.45Co0.05O4)。
The first discharge specific capacity of the manganese-based lithium battery cathode material prepared in the embodiment within the voltage range of 5-3.4V is 132 mA.h.g-1(ii) a And has a stable discharge platform within the range of 4.7-4.6V; when the charge and the discharge are carried out at the multiplying power of 10C, the specific capacity can still keep more than 90 percent of the charge and discharge specific capacity of 0.1C; the retention rate of specific capacity of 200 times of cyclic charge and discharge reaches more than 98 percent, and the specific energy density is 580 W.h.kg-1The above.
Example 2
A preparation method of a manganese-based lithium battery positive electrode material specifically comprises the following steps:
1) deoxidizing and roasting: adding a predetermined amount of manganese dioxide (MnO)2) Feeding into a muffle furnace, roasting at 650 + -50 deg.C for 5 hr in natural atmosphere, naturally cooling to room temperature to obtain Mn2O3Wherein, MnO is2Is commercially available manganese dioxide, in particular high-purity chemical manganese dioxide, and the particle size is in the range of-100 to-50 meshes;
2) disproportionation reaction treatment of hot sulfuric acid solution: the obtained Mn is measured according to the solid-to-liquid ratio of 1: 52O3Then adding the manganese oxide into a sulfuric acid solution with the mass concentration of 20% for disproportionation, wherein the disproportionation temperature of the disproportionation is 80 ℃, the disproportionation time is 0.5 hour, the disproportionation rate is more than 98% after the disproportionation is finished, and then filtering, washing, drying and weighing are carried out to obtain the active MnO serving as the manganese source precursor2Crystal grains are reserved;
3) adding the manganese source precursor into a container containing a certain amount of mixed saturated solution of lithium nitrate, nickel nitrate and cobalt nitrate according to a preset ratio of Li to Mn to Ni to Co of 1.2 to 0.5 to 0.15, soaking at a constant temperature of 95 ℃ for 5 hours, directly evaporating, drying and grinding, then placing in a muffle furnace, calcining at a temperature of 750 +/-50 ℃ for 8 hours, naturally cooling to room temperature,grinding uniformly to obtain the manganese-based lithium battery cathode material, namely the layered lithium-rich manganese-based multi-element cathode material (Li)1.2Mn0.5Ni0.15Co0.15O2)。
The first discharge specific capacity of the manganese-based lithium battery cathode material prepared in the embodiment is 262mA · h · g within the voltage range of 4.8-2.0V-1(ii) a The specific capacity retention rate of 100-time cyclic charge and discharge reaches over 84 percent; when the charge and discharge are carried out at 5C multiplying power, the specific capacity can still keep more than 50 percent of the charge and discharge specific capacity of 0.1C.
Example 3
A preparation method of a manganese-based lithium battery positive electrode material specifically comprises the following steps:
1) deoxidizing and roasting: adding a predetermined amount of manganese dioxide (MnO)2) Feeding into a muffle furnace, roasting at 650 + -50 deg.C for 5 hr in natural atmosphere, naturally cooling to room temperature to obtain Mn2O3Wherein, MnO is2Is commercially available manganese dioxide, in particular to purified electrolytic manganese anode mud, the particle size is in the range of-200 to-100 meshes;
2) disproportionation reaction treatment of hot sulfuric acid solution: the obtained Mn is measured according to the solid-to-liquid ratio of 1: 52O3Then adding the manganese oxide into a sulfuric acid solution with the mass concentration of 20% for disproportionation, wherein the disproportionation temperature of the disproportionation is 80 ℃, the disproportionation time is 0.5 hour, the disproportionation rate is more than 98% after the disproportionation is finished, and then filtering, washing, drying and weighing are carried out to obtain the active MnO serving as the manganese source precursor2Crystal grains are reserved;
3) adding the manganese source precursor into a container containing a mixed solution of nickel sulfate and cobalt sulfate according to a pre-designed ratio of Li, Mn, Ni and Co of 1.2: 0.5: 0.15, wherein the concentration of the mixed solution of nickel sulfate and cobalt sulfate is 2.0mol/L, dropwise adding a potassium hydroxide solution with the concentration of 1.0mol/L according to a preset ratio under the condition of stirring, and adjusting the pH of the mixed solution to be alkalescent (7)<pH<11) With MnO of2Crystal grains form coprecipitation, the coprecipitation reaction is finished within 0.5 hour, then, the ternary precursor is obtained through the working procedures of filtering, washing, drying and the like, and less generation is generated in the processAn amount of wastewater;
4) mixing and grinding lithium hydroxide powder and the prepared ternary precursor according to a pre-designed ratio of Li to Mn to Ni to Co of 1.2 to 0.5 to 0.15, placing the mixture in a muffle furnace, calcining the mixture for 12 hours at the temperature of 750 +/-50 ℃, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the manganese-based lithium battery cathode material, namely the layered lithium-rich manganese-based multi-element cathode material (Li, Mn: Ni: Co)1.2Mn0.5Ni0.15Co0.15O2)。
The first discharge specific capacity of the manganese-based lithium battery cathode material prepared in the embodiment is 274mA · h · g within the voltage range of 4.8-2.0V-1(ii) a The specific capacity retention rate of 100 times of cyclic charge and discharge reaches more than 85 percent; when the charge and discharge are carried out at 5C multiplying power, the specific capacity can still keep more than 50 percent of the charge and discharge specific capacity of 0.1C.
Example 4
A preparation method of a manganese-based lithium battery positive electrode material specifically comprises the following steps:
1) deoxidizing and roasting: adding a predetermined amount of manganese dioxide (MnO)2) Feeding into a muffle furnace, roasting at 650 + -50 deg.C for 5 hr in natural atmosphere, naturally cooling to room temperature to obtain Mn2O3Wherein, MnO is2Is commercially available manganese dioxide, in particular electrolytic manganese dioxide, and the particle size is in the range of-200 to-100 meshes;
2) disproportionation reaction treatment of hot sulfuric acid solution: the obtained Mn is measured according to the solid-to-liquid ratio of 1: 52O3Then adding the manganese oxide into a sulfuric acid solution with the mass concentration of 20% for disproportionation, wherein the disproportionation temperature of the disproportionation is 80 ℃, the disproportionation time is 1.0 hour, the disproportionation rate is more than 99% after the disproportionation is finished, and then filtering, washing, drying and weighing are carried out to obtain the active MnO serving as the manganese source precursor2Crystal grains are reserved;
3) adding the manganese source precursor into a container containing a cobalt nitrate saturated solution according to a pre-designed ratio, namely Li, Mn and Co are 1.25: 0.5: 0.25, soaking at a constant temperature of 90 ℃ for 5 hours, directly evaporating and drying, then placing the obtained powdery solid into a muffle furnace, roasting at a temperature of 250 ℃ for 4 hours, cooling and grinding to obtain a multi-element precursor, namely a manganese-cobalt oxide precursor, wherein no wastewater is generated in the process;
4) adding a heat saturated lithium hydroxide solution into the prepared manganese-cobalt oxide precursor according to a pre-designed ratio of Li, Mn and Co, namely 1.25: 0.5: 0.25, soaking in a sealed reactor at 180 ℃ for 8 hours in a heat preservation manner, evaporating, drying and grinding, putting in a muffle furnace, calcining at 500 +/-50 ℃ for 10 hours, naturally cooling to room temperature, and grinding uniformly to obtain the manganese-based lithium battery anode material, namely the layered lithium-rich manganese-based binary composite anode material (Li, Mn and Co) (Li, Mn and Co are 1.25: 0.5: 0.25)1.25Mn0.5Co0.25O2)。
The manganese-based lithium battery cathode material prepared in the embodiment has a specific first discharge capacity of 350 mA.h.g within a voltage range of 4.8-2.0V-1Left and right; the specific capacity retention rate of 200 times of cyclic charge and discharge reaches more than 98 percent; when the charge and discharge are carried out at the multiplying power of 10C, the specific capacity can still keep more than 95 percent of the charge and discharge specific capacity of 0.1C.
For MnO in each embodiment of the present invention2Mn obtained after roasting treatment2O3The crystal particles were subjected to SEM characterization, and the results are shown in FIG. 1.
As can be seen from FIG. 1, MnO is generally commercially available2Is converted into Mn by roasting treatment2O3In the process, Mn-O is broken and the crystal shrinks, and a net crystal structure is formed apparently, and the diameter of the net hole is about 0.1 micron.
For MnO in each embodiment of the present invention2Active MnO obtained after roasting and disproportionation2The crystal particles were subjected to SEM characterization, and the results are shown in FIG. 2.
As can be seen from FIG. 2, MnO obtained after disproportionation treatment2Crystal grains not only retain original parent Mn2O3The surface of the net crystal structure is formed into a plurality of nano-sized depressions and stabs due to acid etching, so that a great specific surface area is formed.
Furthermore, it is noted that MnSO is contained in the acid filtrate after disproportionation in the invention4Has high content and can be comprehensively utilized.The acidic filtrate after disproportionation can be repeatedly used in the subsequent disproportionation process to form a solid-liquid countercurrent step utilization process until the MnSO in the solid-liquid countercurrent step utilization process4The concentration is higher or the content of residual acid is less than 3 percent, then proper amount of manganese carbonate is added to react to be neutral, and MnSO is obtained after purification4The solution can be reused as a raw material for producing electrolytic manganese dioxide or chemical manganese dioxide.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The manganese source precursor for the manganese-based lithium battery cathode material is characterized by consisting of MnO2Sequentially carrying out deoxidation roasting and disproportionation reaction of hot sulfuric acid solution to obtain active MnO2And (4) crystal grains.
2. The manganese source precursor for a positive electrode material for a manganese-based lithium battery according to claim 1, wherein said MnO is2Is one or more of electrolytic manganese dioxide, chemical manganese dioxide and purified electrolytic manganese anode mud.
3. A method for preparing a manganese source precursor for a positive electrode material for a manganese-based lithium battery according to claim 1 or 2, comprising the steps of:
1) deoxidizing and roasting: MnO of2Roasting for 3-10 h under the conditions of natural atmosphere and temperature of 570-850 ℃, and naturally cooling to normal temperature to obtain Mn2O3；
2) Disproportionation reaction treatment of hot sulfuric acid solution: mixing the Mn with a solid-liquid ratio of 1: 4-82O3Adding the precursor into a sulfuric acid solution for disproportionation, and after the disproportionation is finished, filtering, washing and drying to obtain active MnO as a manganese source precursor2And (4) crystal grains.
4. The method for preparing the manganese source precursor for the positive electrode material of the manganese-based lithium battery according to claim 3, wherein the mass concentration of the sulfuric acid solution in the step 2) is 10% to 50%; the disproportionation temperature of the disproportionation treatment in the step 2) is 50-100 ℃, and the disproportionation reaction time is 0.5-4 h.
5. The manganese-based lithium battery positive electrode material is prepared by blending the manganese source precursor of claim 1 or 2 and preset synthetic elements according to a certain component proportion, then carrying out impregnation, evaporation dehydration, drying and calcination, wherein the preset synthetic elements comprise Li and one or more of Ni, Co, Fe, Cr, Al, La and Ce; or the manganese source precursor of claim 1 is mixed with preset synthetic elements according to a certain component proportion, then the mixture is prepared into a multi-element precursor by adopting an impregnation method or a coprecipitation method, and the multi-element precursor is mixed with a lithium source and then calcined, wherein the preset synthetic elements comprise one or more of Ni, Co, Fe, Cr, Al, La and Ce.
6. The manganese-based lithium battery positive electrode material according to claim 5, wherein the manganese-based lithium battery positive electrode material is a layered lithium-rich positive electrode material or a non-lithium-rich positive electrode material; the chemical formula of the layered lithium-rich cathode material is (1-x) Li2MnO3·xLiMO2Wherein x is more than or equal to 0 and less than or equal to 1.0, and M is one or more of Ni, Co, Mn, Fe, Cr, La, Ce and Al; the chemical formula of the non-lithium-rich cathode material is LiMn2-xMxO4Wherein x is more than or equal to 0 and less than or equal to 0.5, and M is one or more of Ni, Co, Fe, La, Ce, Al and Cr.
7. The manganese-based lithium battery positive electrode material as claimed in claim 5 or 6, wherein the predetermined synthetic element Li is derived from one or more of lithium nitrate, lithium carbonate and lithium hydroxide; the preset synthetic element Ni is derived from one or more of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel carbonate and nickel oxalate; the preset synthetic element Co is derived from one or more of cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt oxalate and cobalt acetate; the preset synthetic element Fe is derived from one or more of ferric nitrate, ferric sulfate, ferric chloride, ferric acetate and ferric oxalate; the preset synthetic element Cr is from one of chromium nitrate, chromium sulfate and chromium chloride; the preset synthetic element Al is derived from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the preset synthesis element La is derived from one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate; the preset synthetic element Ce is derived from one or more of cerium nitrate, cerium acetate, cerium carbonate and cerium chloride.
8. A method for preparing a positive electrode material for a manganese-based lithium battery according to claim 5 or 6 or 7, comprising the steps of:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, soaking for 0.5-12 h at 60-120 ℃, evaporating, dehydrating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery anode material.
9. A method for preparing a positive electrode material for a manganese-based lithium battery according to claim 5 or 6 or 7, comprising the steps of:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, preserving heat and impregnating for 0.5-12 h at the temperature of 60-120 ℃, evaporating, dehydrating, drying, decomposing and roasting for 1-8 h at the temperature of 125-280 ℃, cooling, and grinding to obtain a multi-element precursor;
adding a lithium source into the multi-element precursor, soaking for 3-10 h at 100-250 ℃, evaporating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery cathode material.
10. A method for preparing a positive electrode material for a manganese-based lithium battery according to claim 5 or 6 or 7, comprising the steps of:
adding the manganese source precursor into a soluble salt solution containing the preset synthetic elements, adding a potassium hydroxide or sodium hydroxide solution under the stirring condition, adjusting the pH of the solution to 7 to less than pH 11, carrying out coprecipitation reaction, and after the coprecipitation reaction is finished, filtering, washing and drying to obtain a multi-element precursor;
adding a lithium source into the multi-element precursor, soaking for 3-10 h at 100-250 ℃, evaporating, drying, grinding, then calcining for 5-24h at 400-950 ℃, naturally cooling to room temperature, and grinding to obtain the manganese-based lithium battery cathode material.
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Application publication date: 20200828