CN106784726B - Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof - Google Patents

Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof Download PDF

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CN106784726B
CN106784726B CN201710033546.0A CN201710033546A CN106784726B CN 106784726 B CN106784726 B CN 106784726B CN 201710033546 A CN201710033546 A CN 201710033546A CN 106784726 B CN106784726 B CN 106784726B
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李东林
李童心
张巍
樊小勇
苟蕾
张世龙
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Changan University
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Abstract

The invention discloses a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material with a chemical general formula of xLi2MnO3·(1‑x)LiMO2·yLiVOPO4Wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is Mn, Co and Ni, and y accounts for 0.1-99 percent of x; comprises a manganese raw material, a nickel raw material, a cobalt raw material, lithium salt, a phosphorus source, a vanadium source, a complexing agent and a reducing agent. The preparation method comprises the following steps: the method comprises the steps of preparing a lithium-rich manganese-based layered lithium ion battery anode material and a lithium vanadyl phosphate precursor by a sol-gel method, and preparing a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material by a sol-gel liquid phase coating method or a grinding solid phase coating method. The method improves the electrochemical stability and the cycling stability of the lithium ion battery anode material by utilizing the characteristics of high energy density, stable platform, slow attenuation and the like of the lithium vanadyl phosphate, obviously improves the rate capability and solves the problem of platform attenuation.

Description

Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery preparation, in particular to a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material and a preparation method thereof.
Background
The energy crisis and environmental pollution have become serious threats for human sustainable development, and the development of renewable energy is imperative. The full development of clean energy sources such as solar energy, wind energy, hydrogen energy, tidal energy and the like has very important significance for the global sustainable development. However, these energies are not continuous, so that a chemical source of electricity is very important as a means of converting and storing energy.
Is portableIn the electronic devices, lithium ion batteries having high energy density, light weight, and reliable safety are applied on a large scale. For lithium ion batteries, the positive electrode material has been the core part. To date, LiCoO2The cathode material is widely applied to commercial lithium ion batteries, is easy to prepare, has good electrochemical performance, and only shows half of theoretical capacity (140 mAh.g)-1) And Co is a toxic and very expensive element, the problems of high cost and toxicity are both limitations of LiCoO2Becomes a factor of an ideal anode material. LiMn2O4Is a typical spinel-structured positive electrode material, spinel LiMn2O4Having a specific LiCoO ratio2Low cost, low toxicity and high rate capability; however, the spinel LiMn2O4The capacity of (2) is severely attenuated, and especially at high temperature, the provided capacity is slightly lower, and is only 120mAh g-1Left and right. LiFePO4The main direction is power batteries, Fe is abundant in nature, has lower toxicity than Co, Ni and Mn, and has long service life, safety, high temperature resistance and other excellent characteristics, so that the Fe-Ni-Mn alloy is concerned. However, LiFePO4The material has low electronic conductivity (10) at room temperature-9S/cm), poor conductivity, low tap density, poor low temperature performance, and equal capacity of lithium iron phosphate batteries, which are larger than lithium ion batteries such as lithium cobaltate batteries, and thus have no advantages in the aspect of micro batteries, and the above disadvantages limit their wide application.
How to reduce the cost, improve the safety and increase the capacity becomes a main problem of research work. After a lot of research, researchers replace Co with Ni and Mn to prepare a layered anode material Li [ Li ]0.2Mn0.54Ni0.13Co0.13]O2The lithium-rich manganese-based cathode material is called as a lithium-rich manganese-based cathode material because the Mn element occupies a large content. Among the positive electrode materials that have been studied, the lithium-rich positive electrode material xLi2MnO3·(1-x)LiMO2Can provide 230mAh g at the working voltage of more than 2.5V-1The above high capacity is the most promising new generation of positive electrode material. WhereinThe function of Co can reduce the mixed occupation of cations, effectively stabilize the layered structure of the material, reduce the impedance value and improve the conductivity. Mn is introduced, so that not only can the material cost be reduced, but also the safety and the stability of the material can be improved; the introduction of Ni can increase the capacity of the material.
In the existing lithium-rich manganese-based layered cathode material, Li+The ion diffusion coefficient is very low and is only 10-14cm2s-1Left and right, so that the electronic conductivity of the material is very low. Therefore, the material still has a plurality of problems to be solved: low efficiency for the first time, poor high rate performance due to low electronic conductance, poor long cycle stability, platform attenuation, and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the lithium vanadyl phosphate modified lithium-rich manganese-based layered cathode material which has slow decay of a discharge platform and good rate capability.
The invention also aims to provide the lithium vanadyl phosphate modified lithium-rich manganese-based layered cathode material and the preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The (mono) lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material is characterized in that the chemical general formula of the material is xLi2MnO3·(1-x)LiMO2·yLiVOPO4Wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is Mn, Co and Ni, and y accounts for 0.1-99 percent of x.
The lithium vanadyl (di) phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material is characterized by comprising the following raw material components: manganese raw material, nickel raw material, cobalt raw material, lithium salt, phosphorus source, vanadium source, complexing agent and reducing agent.
Preferably, the manganese raw material is metal manganese, manganese oxide, manganese-containing inorganic salt, manganese-containing organic salt or manganese-containing alkoxide.
Further preferably, the manganese raw material is manganese acetate, manganese nitrate, manganese sulfate, manganese formate or manganese acetate.
Preferably, the nickel raw material is metallic nickel, nickel oxide, nickel-containing inorganic salt, nickel-containing organic salt or nickel-containing alkoxide.
Further preferably, the nickel raw material is nickel acetate, nickel nitrate, nickel sulfate, nickel formate or nickel acetate.
Preferably, the cobalt raw material is metallic cobalt, cobalt oxide, cobalt-containing inorganic salt, cobalt-containing organic salt or cobalt-containing alkoxide.
Further preferably, the cobalt raw material is cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt formate or cobalt acetate.
Preferably, the lithium salt is lithium oxide, lithium-containing inorganic salt, lithium-containing organic salt, or lithium-containing alkoxide.
Further preferably, the lithium salt is lithium nitrate, lithium acetate, lithium formate, lithium hydroxide or lithium carbonate.
Preferably, the phosphorus source is a phosphorus-containing organophosphate or a phosphorus-containing organophosphate.
Further preferably, the phosphorus source is ammonium dihydrogen phosphate, ammonium metaphosphate, phosphoric acid, or triethyl phosphate.
Preferably, the vanadium source is vanadium oxide, organic vanadate ester.
Further preferably, the vanadium source is vanadium pentoxide or ammonium vanadate.
Preferably, the complexing agent is an alcohol amine complexing agent, a hydroxycarboxylic acid complexing agent, an organic phosphate complexing agent or a polyacrylic acid complexing agent.
Further preferably, the complexing agent is citric acid, acetylacetone, ethylenediaminetetraacetic acid, sucrose, or glucose.
Preferably, the reducing agent is an organic acid reducing agent, an inorganic acid reducing agent or an alcohol reducing agent.
Further preferably, the reducing agent is oxalic acid, citric acid, nitric acid.
Preferably, among the lithium salt, the manganese raw material, the nickel raw material and the cobalt raw material, Li+、Mn2+、Ni2+And Co2+The molar ratio of (1.1-1.9): (0.3997-0.9333): (0.2997-0.0333): (0.2997-0.0333).
Preferably, the molar ratio of the M to the complexing agent is 1: 1-1: 2.
(III) a preparation method of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which is characterized by comprising the following steps:
step 1, preparing a lithium-rich manganese-based layered lithium ion battery anode material by adopting a sol-gel method: dissolving a manganese raw material, a nickel raw material and a cobalt raw material in a liquid solvent in sequence, adding a complexing agent and a lithium salt, heating in a water bath, stirring for reaction to obtain precursor sol, keeping the temperature at 100 ℃ for 24-36h, and finally performing heat treatment to obtain a lithium-rich manganese-based layered lithium ion battery anode material;
step 2, preparing a lithium vanadyl phosphate solution by adopting a sol-gel method: dissolving a vanadium source and a reducing agent in a liquid solvent, adding a lithium salt and a phosphorus source, heating in a water bath, and stirring for reaction to form sol, thereby obtaining a lithium vanadyl phosphate solution;
step 3, preparing the lithium vanadium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material by adopting a sol-gel liquid phase coating method: adding the lithium-rich manganese-based layered positive electrode material into a lithium vanadyl phosphate solution, stirring, carrying out ultrasonic treatment and negative pressure impregnation to obtain a precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material, finally drying the precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material in air at 70 ℃ for 12-24h, and carrying out heat treatment to obtain the lithium-rich manganese-based layered lithium ion battery positive electrode material.
Preferably, in the step 1, the temperature of the water bath heating is 50-90 ℃, and the stirring reaction time is 3-5 h.
Preferably, in step 1, the heat treatment is performed according to the following operations: calcining for 5 hours at the temperature of 450 ℃ and calcining for 12 hours at the temperature of 900 ℃ in sequence in a muffle furnace under the air atmosphere.
Preferably, in step 1 and step 2, the liquid solvent is deionized water.
Preferably, in the step 2, the temperature of the water bath heating is 70-80 ℃, and the stirring reaction time is 0.5-2 h.
Preferably, in the step 3, the vacuum pressure for the negative pressure impregnation is 0.05-0.08MPa, and the time is 1-12 h.
Preferably, in step 3, the heat treatment is performed according to the following operations: calcining for 4 hours at 300 ℃ and calcining for 4 hours at 500 ℃ in sequence in a muffle furnace under the air atmosphere.
(IV) the preparation method of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material is characterized by comprising the following steps of:
step 1, preparing a lithium-rich manganese-based layered lithium ion battery anode material by adopting a sol-gel method: dissolving a manganese raw material, a nickel raw material and a cobalt raw material in a liquid solvent in sequence, adding a complexing agent and a lithium salt, heating in a water bath, stirring for reaction to obtain precursor sol, keeping the temperature at 100 ℃ for 24-36h, and finally performing heat treatment to obtain a lithium-rich manganese-based layered lithium ion battery anode material;
step 2, preparing a lithium vanadyl phosphate precursor by adopting a sol-gel method: dissolving a vanadium source and a reducing agent in a liquid solvent, adding a lithium salt and a phosphorus source, heating in a water bath, stirring for reaction to form sol, and drying to obtain lithium vanadyl phosphate precursor powder.
Step 3, preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material by adopting a grinding solid-phase coating method: and mixing the lithium-rich manganese-based layered lithium ion battery positive electrode material with the lithium vanadyl phosphate precursor powder, uniformly grinding, and performing heat treatment to obtain the lithium-rich manganese-based layered lithium ion battery positive electrode material.
Preferably, in the step 1, the temperature of the water bath heating is 50-90 ℃, and the stirring reaction time is 3-5 h.
Preferably, in step 1 and step 2, the liquid solvent is deionized water.
Preferably, in step 1, the heat treatment is performed according to the following operations: calcining for 5 hours at the temperature of 450 ℃ and calcining for 12 hours at the temperature of 900 ℃ in sequence in a muffle furnace under the air atmosphere.
Preferably, in the step 1, the temperature of the water bath heating is 70-80 ℃, and the stirring reaction time is 0.5-2 h.
Preferably, in step 2, the temperature for drying is 50-100 ℃.
Preferably, in step 3, the grinding time is 2-5 h.
Preferably, the heat treatment is performed as follows: calcining for 4 hours at 300 ℃ and calcining for 4 hours at 500 ℃ in sequence in a muffle furnace under the air atmosphere.
Compared with the prior art, the invention has the beneficial effects that:
according to the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material prepared by the invention, the characteristics of high energy density, stable platform, slow attenuation and the like of lithium vanadyl phosphate are utilized, so that the electrochemical stability and the cycle stability of the lithium ion battery cathode material are improved, the rate capability of the lithium ion battery cathode material is obviously improved, and the problem of platform attenuation is solved.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is a scanning electron micrograph of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material of example 7;
FIG. 2 is a graph of the first 9 times of charge and discharge of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material of example 7 at 0.1C; in the figure, the abscissa is the specific capacity (specific capacity) of the material in mAh/g, and the ordinate is the voltage (voltage) in V;
FIG. 3 is a scanning electron micrograph of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material of example 8;
FIG. 4 is a graph of the previous 9 charge-discharge cycles of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material of example 8 at 0.1C; in the figure, the abscissa is the specific capacity (specific capacity) of the material in mAh/g, and the ordinate is the voltage (voltage) in V.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following steps of:
(1) dissolving 0.03997mol of manganese acetate, 0.02997mol of cobalt acetate and 0.02997mol of nickel acetate in 100mL of deionized water in sequence, adding 0.09mol of citric acid and 0.11mol of lithium nitrate, adjusting the pH value to 9 by using ammonia water, stirring for 3 hours under the condition of 80 ℃ water bath to form precursor sol, keeping the temperature of 100 ℃ in air for 24 hours, calcining in a muffle furnace, calcining at the temperature of 450 ℃ for 5 hours in sequence, and calcining at the temperature of 900 ℃ for 12 hours; and obtaining the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.000135mol of oxalic acid, dissolving in 100mL of deionized water, adding 0.000045mol of vanadium pentoxide, stirring for 2h at 70 ℃ in a water bath, adding 0.00009mol of lithium nitrate, and finally adding 0.00009mol of ammonium dihydrogen phosphate, and reacting to obtain a lithium vanadyl phosphate precursor.
(3) Weighing 1g of the lithium-rich manganese-based layered lithium ion battery anode material in the step (1), adding the lithium-rich manganese-based layered lithium ion battery anode material into a vanadium-oxygen lithium phosphate precursor, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 12h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium-oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material in air at 70 ℃ for 12-24h, calcining in a muffle furnace, and processing at 300 ℃, 4h, 500 ℃ and 4h to obtain 0.95g of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.1Li2MnO3·0.9LiMn0.333Co0.333Ni0.333O2]·0.0009LiVOPO4。
Example 2
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following specific steps of:
(1) 0.03997mol of manganese acetate, 0.02997mol of cobalt nitrate and 0.02997mol of nickel nitrate are sequentially dissolved in 100mL of deionized water, 0.09mol of citric acid and 0.11mol of lithium nitrate are added, then ammonia water is used for adjusting the pH value to 7, the mixture is stirred for 4 hours under the condition of 80 ℃ water bath to form precursor sol, and the temperature is kept for 36 hours at 100 ℃ in the air. Calcining in a muffle furnace at 450 deg.C for 5 hr, 900 deg.C for 12 hr. And obtaining the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.045mol of ammonium vanadate, dissolving the ammonium vanadate in 100mL of deionized water, stirring the solution for 2 hours at the temperature of 70 ℃ in a water bath, adding 0.045mol of lithium nitrate, and finally adding 0.045mol of ammonium dihydrogen phosphate, and reacting to obtain the lithium vanadyl phosphate sol.
(3) Adding the lithium-rich manganese-based layered lithium ion battery positive electrode material into the vanadium-oxygen lithium phosphate sol, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 12h under the vacuum pressure of 0.05-0.08MPa, and drying to obtain a vanadium-oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor;
(4) drying the obtained precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material in air at 70 ℃ for 24h, calcining in a muffle furnace, and processing at 600 ℃ for 5h to obtain 0.95g of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.1Li2MnO3·0.9LiMn0.333Co0.333Ni0.333O2]·0.45LiVOPO4。
Example 3
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following specific steps of:
(1) 0.03997mol of manganese acetate, 0.02997mol of cobalt nitrate and 0.02997mol of nickel nitrate are sequentially dissolved in 100mL of deionized water, 0.18mol of citric acid is added, 0.11mol of lithium nitrate is added, then the pH value is adjusted to 8 by ammonia water, the mixture is stirred for 4 hours under the condition of 80 ℃ water bath to form precursor sol, and the precursor sol is kept at 100 ℃ in the air for 24 hours. Calcining in a muffle furnace at 450 deg.C for 5 hr, 900 deg.C for 12 hr. And obtaining the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.13365mol of citric acid, dissolving the citric acid in 100mL of deionized water, adding 0.04455mol of vanadium pentoxide, stirring for 2h under the condition of 80 ℃ water bath, adding 0.0891mol of lithium acetate, finally adding 0.0891mol of ammonium dihydrogen phosphate, and reacting to obtain a vanadium oxygen lithium phosphate precursor solution.
(3) Adding the lithium-rich manganese-based layered lithium ion battery anode material in the step (1) into a vanadium oxygen lithium phosphate precursor solution, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 6h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor in air at 70 ℃ for 12h, calcining in a muffle furnace, and processing at 600 ℃ for 5h to obtain the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.1Li2MnO3·0.9Li Mn0.333Co0.333Ni0.333O2]·0.891LiVOPO4。
Example 4
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery secondary anode material, which comprises the following specific steps of:
(1) 0.09333mol of manganese nitrate, 0.0033mol of cobalt nitrate and 0.0033mol of nickel nitrate are sequentially dissolved in 150mL of ethylene glycol ethyl ether, a transparent solution is formed in a 50 ℃ water bath, then 0.2mol of acetylacetone and 0.19mol of lithium nitrate are sequentially added, the temperature is raised to 80 ℃ under the water bath condition, stirring and evaporation are carried out, precursor sol is formed, and the temperature is maintained for 36h at 120 ℃ under the condition of 100 plus materials in the air. Calcining in a muffle furnace at 450 deg.C for 5 hr, 900 deg.C for 12 hr. And obtaining the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.00001mol of ammonium vanadate, dissolving in 100mL of deionized water, stirring for 30min under the condition of 80 ℃ water bath, dripping 0.00001mol of diluted phosphoric acid, finally adding 0.00001mol of lithium nitrate, and reacting to obtain the lithium vanadyl phosphate precursor solution.
(3) Adding the lithium-rich manganese-based layered lithium ion battery anode material in the step (1) into a vanadium oxygen lithium phosphate solution, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 6h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor in air at 80 ℃ for 24h, calcining in a muffle furnace, and processing at 600 ℃ for 5h to obtain the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.9Li2MnO3·0.1Li Mn0.333Co0.333Ni0.333O2]·0.0001LiVOPO4。
Example 5
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered cathode material, which comprises the following specific steps of:
(1) sequentially dissolving 0.09333mol of manganese acetate, 0.00333mol of cobalt acetate and 0.00333mol of nickel acetate in 100mL of deionized water, and stirring in a water bath at 50 ℃ to form a transparent aqueous solution; dissolving 0.1mol of sodium carbonate in 50mL of deionized water to form a sodium carbonate aqueous solution; dissolving 0.1mol of ammonium bicarbonate in 50mL of deionized water to form an ammonium bicarbonate aqueous solution; three phases of the three solutions are in parallel flow, the flow rate is controlled, the three solutions are simultaneously dropped into a deionized water solution with pH of 9 and a small amount of ammonia water at the same flow rate, the three solutions are violently stirred for 7 hours under the condition of 50 ℃ water bath, then are precipitated for 12 hours, filtered and dried; and grinding the powder obtained by filtering and 0.095mol of lithium carbonate, placing the powder in a muffle furnace, and calcining the powder for 15 hours at 900 ℃ to obtain the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.0005mol of ammonium vanadate, dissolving the ammonium vanadate in 100mL of deionized water, stirring the solution for 30min under the condition of 80 ℃ water bath, dripping 0.0005mol of diluted phosphoric acid, and finally adding 0.0005mol of lithium nitrate to react to obtain the lithium vanadyl phosphate precursor solution.
(3) Adding the lithium-rich manganese-based layered lithium ion battery anode material in the step (1) into a vanadium oxygen lithium phosphate solution, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 1h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor in air at 80 ℃ for 24h, calcining in a muffle furnace, and processing at 600 ℃ for 5h to obtain the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.9Li2MnO3·0.1Li Mn0.333Co0.333Ni0.333O2]·0.05LiVOPO4。
Example 6
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following specific steps of:
(1) 0.09333mol of manganese acetate, 0.00333mol of cobalt acetate and 0.00333mol of nickel acetate are sequentially dissolved in 100mL of deionized water, 0.19mol of lithium nitrate is added, 0.2mol of cane sugar is added, the mixture is stirred for 5 hours under the condition of 80 ℃ water bath to form precursor sol, and the precursor sol is kept at 100 ℃ in the air for 24 hours. Calcining in a muffle furnace at 450 deg.C for 5 hr, 900 deg.C for 12 hr. And obtaining the lithium-rich manganese-based layered lithium ion battery anode material which is powdery.
(2) Weighing 0.0165mol of oxalic acid, dissolving in 20mL of deionized water, adding 0.00495mol of vanadium pentoxide, stirring for 2h under the condition of 70 ℃ water bath, adding 0.0099mol of lithium nitrate, and finally adding 0.0099mol of ammonium dihydrogen phosphate, and reacting to obtain a vanadium oxygen lithium phosphate solution.
(3) Adding the lithium-rich manganese-based layered lithium ion battery anode material in the step (1) into a vanadium oxygen lithium phosphate solution, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 1h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor in air at 70 ℃ for 12h, calcining in a muffle furnace at the temperature of 300 ℃, 4h, 500 DEG, removing the impurities,4h, obtaining 0.95g of lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has the chemical formula of 0.9Li2MnO3·0.1LiMn0.333Co0.333Ni0.333O2]·0.099LiVOPO4。
Example 7
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following specific steps of:
(1) 0.0533mol of manganese acetate, 0.0233mol of cobalt acetate and 0.0233mol of nickel acetate are sequentially dissolved in 100mL of deionized water, 0.07mol of citric acid is added, 0.13mol of lithium nitrate is added, then the pH value is adjusted to 8 by ammonia water, the mixture is stirred for 5 hours under the condition of 80 ℃ water bath to form precursor sol, and the precursor sol is kept at 100 ℃ in the air for 36 hours. Calcining in a muffle furnace at 450 deg.C for 5 hr, 900 deg.C for 12 hr. The manganese-based multi-element substrate cathode material is obtained and is in a powder shape.
(2) Weighing 0.0105mol of oxalic acid, dissolving in 100mL of deionized water, adding 0.0035mol of vanadium pentoxide, stirring for 2 hours at 70 ℃ in a water bath, adding 0.007mol of lithium nitrate, and finally adding 0.007mol of ammonium dihydrogen phosphate, and reacting to obtain a lithium vanadyl phosphate solution.
(3) Adding the lithium-rich manganese-based layered lithium ion battery anode material obtained in the step (1) into a vanadium-oxygen lithium phosphate solution, stirring for 30min, performing ultrasonic treatment for 30min, performing negative pressure impregnation for 6h, wherein the vacuum pressure is 0.05-0.08MPa, and drying to obtain a vanadium-oxygen lithium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor;
(4) drying the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material precursor in air at 70 ℃ for 24h, calcining in a muffle furnace, and processing at 300 ℃, 4h, 500 ℃ and 4h to obtain the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material which is powdery and has a chemical formula of [0.3Li2MnO3·0.7LiMn0.333Co0.333Ni0.333O2]·0.07LiVOPO4。
Example 8
The invention relates to a preparation method of a lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material, which comprises the following specific steps of:
(1) the same procedure as that for preparing the lithium-rich manganese-based layered lithium ion battery cathode material powder in the step (1) in the example 7 was repeated.
(2) Weighing 0.0105mol of oxalic acid, dissolving in 100mL of deionized water, adding 0.0035mol of vanadium pentoxide, stirring for 2 hours at 70 ℃ in a water bath, adding 0.007mol of lithium nitrate, finally adding 0.007mol of ammonium dihydrogen phosphate, stirring until the solvent is completely evaporated, and reacting to obtain the vanadium oxy lithium phosphate precursor green powder.
(3) And (3) mixing and grinding the lithium-rich manganese-based layered lithium ion battery anode material in the step (1) and the green powder of the lithium vanadyl phosphate precursor obtained in the step (2).
(4) Calcining the precursor of the obtained lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material in a muffle furnace, and treating the temperature at 300 ℃, 4h, 500 ℃ and 4h to obtain the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material which is powdery and has a chemical formula of [0.3Li2MnO3·0.7Li Mn0.333Co0.333Ni0.333O2]·0.07LiVOPO4。
In the invention, the electrochemical performance of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material of all the embodiments is detected.
The electrochemical performance of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material prepared in example 7 is described in combination with the accompanying drawings, and the characterization results are as follows:
fig. 1 is a scanning electron micrograph of a lithium vanadyl phosphate-modified lithium-rich manganese-based layered positive active material prepared in example 7. As can be seen from the figure, the particle diameter of the finally prepared lithium vanadyl phosphate modified lithium-rich manganese-based layered positive electrode active material is about 200 nm.
Fig. 2 is a graph showing the charge and discharge curves of the lithium vanadyl phosphate modified lithium-rich manganese-based layered positive active material prepared in example 7 for the first 9 times at 0.1C, with the abscissa being the specific capacity (specific capacity) of the material in mAh/g and the ordinate being the voltage (voltage) in V; in the figure, the charging data of cycles 1, 4, 7, and 9 are shown in an ascending trend, and the discharging data of cycles 1, 4, 7, and 9 are shown in a descending trend. As can be seen from the figure, the first discharge platform of the lithium ion battery anode active material is above 2.8V, and the discharge platform is slowly attenuated and hardly attenuated along with the charging and discharging, the first discharge specific capacity is 253mAh/g, and the discharge specific capacity is still 235mAh/g after the charging and discharging are carried out for 9 times. And the discharge specific capacity is almost not attenuated from the process of 2 to 9.
In the embodiment 7 of the invention, the electrochemical stability and the rate capability of the lithium-rich manganese-based layered lithium ion battery anode material are improved by utilizing the characteristic of stable electrochemical reaction platform of lithium vanadyl phosphate, so that the modified electrode material with stable circulation is obtained.
The lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material prepared in the examples 1 to 6 has the electrochemical performance equivalent to that of the example 7, and also has the advantages of good rate performance and stable cycle.
Fig. 3 is a scanning electron micrograph of the lithium vanadyl phosphate-modified lithium-rich manganese-based layered positive active material prepared in example 7. As can be seen from the figure, the particle diameter of the finally prepared lithium vanadyl phosphate modified lithium-rich manganese-based layered positive electrode active material is about 200 nm.
Fig. 4 is a graph of the first 9 charge and discharge cycles of the lithium vanadyl phosphate modified lithium-rich manganese-based layered cathode active material prepared in example 8 at 0.1C. The abscissa is the specific capacity (sepecific capacity) of the material in mAh/g, and the ordinate is the voltage (voltage) in V; in the figure, the charging data of cycles 1, 4, 7, and 9 are shown in an ascending trend, and the discharging data of cycles 1, 4, 7, and 9 are shown in a descending trend. As can be seen from the figure, the first discharge platform of the lithium ion battery anode active material is above 2.8V, and the discharge platform is slowly attenuated and hardly attenuated along with the charging and discharging, the first discharge specific capacity is 252mAh/g, and the discharge specific capacity is 245mAh/g after the charging and discharging are carried out for 9 times. And the discharge specific capacity is almost not attenuated from the process of 2 to 9.
In the embodiment 8 of the invention, the electrochemical stability and rate capability of the lithium-rich manganese-based layered lithium ion battery anode material are improved by utilizing the characteristic of stable electrochemical reaction platform of lithium vanadyl phosphate, so that the modified electrode material with stable circulation is obtained.
Obviously, the lithium-rich manganese-based layered lithium ion battery anode material is modified by lithium vanadyl phosphate, so that the problems of platform attenuation and specific capacity attenuation in the discharging process can be relieved, and the cycling stability of the lithium-rich manganese-based layered lithium ion battery anode material is improved to a certain extent.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The preparation method of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material is characterized in that the chemical general formula xLi of the lithium-rich manganese-based layered lithium ion battery anode material2MnO3·(1-x)LiMO2·yLiVOPO4Wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is Mn, Co and Ni, and y accounts for 0.1 to 99 percent of x;
the preparation method comprises the following steps:
step 1, preparing a lithium-rich manganese-based layered lithium ion battery anode material: dissolving a manganese raw material, a nickel raw material and a cobalt raw material in a liquid solvent in sequence, adding a complexing agent and a lithium salt, heating in a water bath, stirring for reaction to obtain precursor sol, keeping the temperature at 100 ℃ for 24-36h, and finally performing heat treatment to obtain a lithium-rich manganese-based layered lithium ion battery anode material;
step 2, preparing a lithium vanadyl phosphate solution: dissolving a vanadium source and a reducing agent in a liquid solvent, adding a lithium salt and a phosphorus source, heating in a water bath, and stirring for reaction to form sol, thereby obtaining a lithium vanadyl phosphate solution;
step 3, preparing the lithium vanadium phosphate modified lithium-rich manganese-based layered lithium ion battery anode material by adopting a sol-gel liquid phase coating method: adding the lithium-rich manganese-based layered positive electrode material into a lithium vanadyl phosphate solution, stirring, carrying out ultrasonic treatment and negative pressure impregnation to obtain a precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material, finally drying the precursor of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery positive electrode material in air at 70 ℃ for 12-24h, and carrying out heat treatment to obtain the lithium-rich manganese-based layered lithium ion battery positive electrode material.
2. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 1, wherein the manganese raw material is metal manganese, manganese oxide, manganese-containing inorganic salt, manganese-containing organic salt or manganese-containing alkoxide; the nickel raw material is metal nickel, nickel oxide, nickel-containing inorganic salt, nickel-containing organic salt or nickel-containing alkoxide; the cobalt raw material is metal cobalt, cobalt oxide, cobalt-containing inorganic salt, cobalt-containing organic salt or cobalt-containing alkoxide; the lithium salt is lithium oxide, lithium-containing inorganic salt, lithium-containing organic salt or lithium-containing alkoxide; the phosphorus source is phosphorus-containing organic phosphate or phosphorus-containing organic phosphate; the vanadium source is vanadium oxide, organic vanadate and organic vanadate ester; the complexing agent is an alcamine complexing agent, a hydroxycarboxylic acid complexing agent, an organic phosphate complexing agent or a polyacrylic acid complexing agent; the reducing agent is an organic acid reducing agent, an inorganic acid reducing agent or an alcohol reducing agent.
3. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 1, wherein, among the lithium salt, the manganese raw material, the nickel raw material and the cobalt raw material, Li is selected+、Mn2+、Ni2+And Co2+The molar ratio of (1.1-1.9) to (0.3997-0.9333) to (0.2997-0.0333) to (0.2997-0.0333).
4. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 1, wherein in step 1, the temperature of water bath heating is 50-90 ℃; the stirring reaction time is 3-5 h; the heat treatment is carried out according to the following operations: calcining for 5 hours at the temperature of 450 ℃ and calcining for 12 hours at the temperature of 900 ℃ in sequence in a muffle furnace under the air atmosphere.
5. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 1, wherein in step 2, the water bath heating temperature is 70-80 ℃, and the stirring reaction time is 0.5-2 h.
6. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 1, wherein in step 3, the heat treatment is performed according to the following operations: calcining for 4 hours at 300 ℃ and calcining for 4 hours at 500 ℃ in sequence in a muffle furnace under the air atmosphere.
7. The preparation method of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material is characterized in that the chemical general formula xLi of the lithium-rich manganese-based layered lithium ion battery anode material2MnO3·(1-x)LiMO2·yLiVOPO4Wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is Mn, Co and Ni, and y accounts for 0.1 to 99 percent of x;
the preparation method comprises the following steps:
step 1, preparing a lithium-rich manganese-based layered lithium ion battery anode material: dissolving a manganese raw material, a nickel raw material and a cobalt raw material in a liquid solvent in sequence, adding a complexing agent and a lithium salt, heating in a water bath, stirring for reaction to obtain precursor sol, keeping the temperature at 100 ℃ for 24-36h, and finally performing heat treatment to obtain a lithium-rich manganese-based layered lithium ion battery anode material;
step 2, preparing a lithium vanadyl phosphate precursor: dissolving a vanadium source and a reducing agent in a liquid solvent, adding a lithium salt and a phosphorus source, heating in a water bath, stirring for reaction to form sol, and drying to obtain lithium vanadyl phosphate precursor powder;
step 3, preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery anode material: and mixing the lithium-rich manganese-based layered lithium ion battery positive electrode material with the lithium vanadyl phosphate precursor powder, uniformly grinding, and performing heat treatment to obtain the lithium-rich manganese-based layered lithium ion battery positive electrode material.
8. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 7, wherein in the step 2, the drying temperature is 50-100 ℃; in the step 3, the grinding time is 2-5 h.
9. The preparation method of the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material according to claim 7, wherein the manganese raw material is metal manganese, manganese oxide, inorganic salt containing manganese, organic salt containing manganese or alkoxide containing manganese; the nickel raw material is metal nickel, nickel oxide, nickel-containing inorganic salt, nickel-containing organic salt or nickel-containing alkoxide; the cobalt raw material is metal cobalt, cobalt oxide, cobalt-containing inorganic salt, cobalt-containing organic salt or cobalt-containing alkoxide; the lithium salt is lithium oxide, lithium-containing inorganic salt, lithium-containing organic salt or lithium-containing alkoxide; the phosphorus source is phosphorus-containing organic phosphate or phosphorus-containing organic phosphate; the vanadium source is vanadium oxide, organic vanadate and organic vanadate ester; the complexing agent is an alcamine complexing agent, a hydroxycarboxylic acid complexing agent, an organic phosphate complexing agent or a polyacrylic acid complexing agent; the reducing agent is an organic acid reducing agent, an inorganic acid reducing agent or an alcohol reducing agent.
10. The method for preparing the lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material as claimed in claim 7, wherein, among the lithium salt, the manganese raw material, the nickel raw material and the cobalt raw material, Li+、Mn2+、Ni2+And Co2+The molar ratio of (1.1-1.9) to (0.3997-0.9333) to (0.2997-0.0333) to (0.2997-0.0333).
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