CN109638275B - Selenium and silicate co-doped high-nickel cathode material and preparation method and application thereof - Google Patents

Selenium and silicate co-doped high-nickel cathode material and preparation method and application thereof Download PDF

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CN109638275B
CN109638275B CN201811545120.4A CN201811545120A CN109638275B CN 109638275 B CN109638275 B CN 109638275B CN 201811545120 A CN201811545120 A CN 201811545120A CN 109638275 B CN109638275 B CN 109638275B
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selenium
nickel
lithium
silicate
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CN109638275A (en
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谭强强
夏青
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Langfang green industry technology service center
Institute of Process Engineering of CAS
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Langfang Institute of Process Engineering of CAS
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    • 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
    • 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
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Abstract

The invention relates to a selenium and silicate co-doped high-nickel anode material, and a preparation method and application thereofxM1‑xSea(SiO4)bO2‑a‑bWherein M is at least one of Mn, Co or Al, x is more than or equal to 0.5 and less than 1, a is more than 0 and less than or equal to 0.05, and b is more than 0 and less than or equal to 0.05. The invention utilizes selenium and silicate to dope low-valence anions to the high-nickel anode material, thereby improving the lattice structure of the material; the selenium and the silicate have good synergistic effect, the structural stability of the material under high voltage can be improved, and the electrochemical performance of the high-nickel anode material is obviously improved. The obtained anode material has the first cyclic discharge specific capacity of more than or equal to 185mAh/g and the capacity retention rate of more than or equal to 85 percent at the voltage window of 2.5-4.2V and the current density of 0.1C, and has good application prospect.

Description

Selenium and silicate co-doped high-nickel cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a selenium and silicate co-doped high-nickel anode material as well as a preparation method and application thereof.
Background
With the rapid development of new energy automobiles, the lithium ion battery industry has entered a rapid development stage. The key materials influencing the performance of the lithium ion battery mainly comprise a positive electrode material, a negative electrode material, electrolyte and the like. The positive electrode material is a main factor which currently limits the performance of the battery and also a main factor which accounts for the higher cost of the lithium ion battery, and is close to 40%.
Most of the positive electrode materials studied in recent years mainly include lithium iron phosphate, lithium manganate, ternary materials, and the like. The high nickel anode material has outstanding advantages in cost and comprehensive performance, and has gradually become a mainstream technical route.
In order to further improve the electrochemical performance of the high nickel material, researchers usually modify the material by means of doping, and many documents and patents are reported at home and abroad about the doping modification of the high nickel cathode material.
Peng Yue et al firstly adopt coprecipitation method to prepare LiNi0.6Co0.2Mn0.2O2Then it is further reacted with NH4F mixed and roasted for 5h at the temperature of 450 ℃ to obtain F-doped LiNi0.6Co0.2Mn0.2O2-xFxThe experimental results show that the specific initial discharge capacity of the material is reduced with the increase of the F doping amount, but the cycling stability is improved (Yue P, Wang Z, Li X, et al0.6Co0.2Mn0.2O2cathode materials by low temperature fluorine subsystem, electrochimica Acta,2013,95: 112-. Prepared by a coprecipitation method (Ni) by Chunyan Fu et al0.6Co0.2-xMn0.2Mgx)CO3The precursor is mixed with LiOH to prepare the Mg-doped NCM cathode material, and the initial specific discharge capacity and the cycle performance of the material are improved compared with those of the undoped material (Fu C, Zhou Z, Liu Y, et al0.6Co0.2Mn0.2O2Journal of Wuhan University of Technology-Mater. Sci. Ed.,2011,26(2): 211-215). Xubin et al prepared Ti-doped Li (Ni) using carbonate coprecipitation0.6Co0.2Mn0.2)1-xTixO2The initial specific discharge capacity of the positive electrode material is 172.5mAh g-1And the specific discharge capacity after 10 cycles is 170.5mAh g-1(Xubin, Zhongqu, Zhang Qian. Ti doped LiNi0.6Co0.2Mn0.2O2Functional material 2010: 295-.
CN106654210A discloses a high-nickel anode material of a high-temperature long-cycle lithium ion battery and a preparation method thereof, wherein Nb is taken as a doping element, and Nb2O5Is a coating layer active oxide, and improves the rate capability and the cycle performance of the high-nickel anode material. CN105070907A discloses a high-nickel anode material, wherein Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, Cs, W, Mo, Ru, Rd or lanthanide is doped on the surface of a matrix, and the damage of a washing solution to the surface structure of the matrix material is relieved by doping elements to stabilize the crystal structure of the surface of the matrix, so that the lithium ion battery prepared from the high-nickel anode material has better capacity and cycle performance.
Although the performance of the high-nickel cathode material is improved by doping modification in the above manner, the method still has certain limitations, and the electrochemical performance of the high-nickel cathode material still has room for improvement.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a selenium and silicate co-doped high-nickel cathode material, a preparation method and an application thereof, and the electrochemical performance of the high-nickel cathode material is further improved in a co-doping manner.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a selenium and silicate co-doped high-nickel cathode material, wherein the cathode material is a selenium and silicate co-doped modified high-nickel cathode material with a chemical formula of LiNixM1-xSea(SiO4)bO2-a-bWherein M is at least one of Mn, Co or Al, x is more than or equal to 0.5 and less than 1, a is more than 0 and less than or equal to 0.05, and b is more than 0 and less than or equal to 0.05.
According to the invention, selenium and silicate are utilized to carry out low-valence anion doping on the high-nickel anode material, and a small amount of selenium replaces oxygen atoms, so that the lattice structure of the material can be improved, and the electronic conductivity of the material can be improved; in addition, Se can form a covalent bond with Si in silicate, so that lattice collapse in the lithium extraction and insertion process is inhibited, the structural stability of the material under high voltage is improved, the electrochemical performance of the high-nickel cathode material is further obviously improved, and excellent cycle stability and capacity retention rate are obtained.
According to the invention, x in the formula is in the range of 0.5 ≦ x < 1, and may be, for example, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.99 or 0.999, etc., and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the invention, a in the formula is in the range of 0 < a ≦ 0.05, and may be, for example, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, etc., and the specific values between the above values are not exhaustive for reasons of space and brevity.
According to the invention, b in the formula is in the range of 0 < b ≦ 0.05, and may be, for example, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, etc., and the specific values between the above values are not exhaustive for reasons of space and brevity.
In a second aspect, the invention provides a preparation method of the selenium and silicate co-doped high nickel cathode material according to the first aspect, which includes the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a nickel source, an M source, a selenium source, a silicon source, a precipitator and a complexing agent into a reaction container in a parallel flow manner, controlling the temperature and the pH value, stirring for reaction, and performing solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the positive electrode material obtained in the step (1) with a lithium source, and performing heat treatment to obtain the selenium and silicate co-doped high-nickel positive electrode material.
In the preparation process, all raw materials are according to the chemical formula LiNixM1-xSea(SiO4)bO2-a-bThe compounding is carried out in the proportion defined in (1).
According to the invention, a stirring device is arranged in the reaction vessel in the step (1).
According to the invention, the nickel source in step (1) is nickel nitrate.
Preferably, M in step (1) is at least one of manganese, cobalt or aluminum, and correspondingly, the manganese source is manganese chloride and/or manganese nitrate; the cobalt source is cobalt nitrate and/or cobalt oxalate; the aluminum source is aluminum nitrate and/or sodium metaaluminate.
According to the invention, the selenium source in step (1) is a hydrazine hydrate solution of selenium.
According to the invention, the silicon source in the step (1) is ethyl orthosilicate ethanol solution.
According to the invention, the precipitant in step (1) is sodium hydroxide and/or potassium hydroxide.
According to the invention, the complexing agent in step (1) is ammonia water.
In the step (1), the addition amounts of the precipitant and the complexing agent are adjusted according to actual conditions, as long as the reaction pH of the solution is controlled within the range.
According to the invention, the pH of the solution during the reaction in step (1) is between 10 and 12.5.
According to the invention, the temperature of the reaction of step (1) is 45-75 ℃, for example 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, and the specific values between the above values, are limited to space and for the sake of brevity, and are not exhaustive.
According to the invention, the reaction time of step (1) is 4-16h, for example, 4h, 6h, 8h, 10h, 12h, 14h or 16h, and the specific values between the above values are limited by space and for the sake of brevity, and are not exhaustive.
According to the invention, after the solid-liquid separation in the step (1), the obtained product is washed and dried to obtain the precursor of the cathode material.
According to the invention, the lithium source in step (2) is lithium carbonate and/or lithium hydroxide monohydrate.
According to the present invention, the molar ratio of the lithium element in the lithium source in the step (2) to the metal element in the cathode material precursor is (1-1.2):1, and may be, for example, 1:1, 1.03:1, 1.05:1, 1.08:1, 1.1:1, 1.13:1, 1.15:1, 1.18:1 or 1.2:1, and the specific values therebetween are limited to space and are not exhaustive for the sake of brevity.
The metal elements in the precursor of the positive electrode material are Ni and metal M.
According to the present invention, the heat treatment of step (2) is performed in an oxygen atmosphere.
According to the invention, the heating rate of the heat treatment in step (2) is 1-30 ℃/min, for example, 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, 25 ℃/min or 30 ℃/min, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the heat treatment of step (2) is carried out in two stages, the first stage: sintering at the temperature of 300 ℃ and 500 ℃ for 4-12 h; and a second stage: the product in the first stage is heated to 600-800 ℃ and sintered for 10-20 h.
The temperature of the first stage heat treatment is 300-.
The time of the first stage heat treatment is 4-12h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, and the specific values therebetween are limited by space and for brevity, and the present invention is not exhaustive.
The temperature of the second stage heat treatment is 600-.
The time of the second stage heat treatment is 10-20h, for example, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
As a preferred technical scheme, the preparation method of the selenium and silicate co-doped high-nickel cathode material comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a nickel source, an M source, a selenium source, a silicon source, a precipitator and a complexing agent into a reaction container with a stirring device in a parallel flow manner, controlling the temperature to be 45-75 ℃, the pH value to be 10-12.5, stirring and reacting for 4-16h, and performing solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) mixing the precursor of the cathode material obtained in the step (1) with a lithium source, controlling the molar ratio of the lithium element in the lithium source to the metal element in the precursor to be (1-1.2):1, heating to 300-800 ℃ at the rate of 1-30 ℃/min under the oxygen atmosphere, sintering for 4-12h, then continuing heating to 600-800 ℃ and sintering for 10-20h, and cooling to obtain the selenium and silicate co-doped high-nickel cathode material.
In a third aspect, the invention provides an application of the selenium and silicate co-doped high-nickel cathode material as a cathode material of a lithium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention utilizes selenium and silicate to dope low-valence anions to the high-nickel anode material, improves the lattice structure of the material and improves the structural stability of the material under high voltage.
(2) The doped selenium and silicate have good synergistic effect, the electrochemical performance of the high-nickel anode material can be obviously improved, the initial cyclic discharge specific capacity of the obtained anode material is more than or equal to 185mAh/g under the voltage window of 2.5-4.2V and the current density of 0.1C, and the capacity retention rate of 200 cycles of cycle is more than or equal to 85%.
(3) The preparation method provided by the invention is simple to operate, easy to realize and beneficial to large-scale popularization.
Detailed Description
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.8Co0.1Mn0.1Se0.02(SiO4)0.05O1.93。
The preparation method comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a sodium hydroxide solution and ammonia water, controlling the temperature to be 45 ℃, stirring and reacting for 4 hours at the pH value of 10, and performing solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the cathode material obtained in the step (1) with lithium hydroxide monohydrate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.1:1, heating to 400 ℃ at the speed of 10 ℃/min in an oxygen atmosphere, sintering for 10h, continuing heating to 600 ℃ and preserving heat for 20h, and cooling to room temperature along with a furnace after sintering is completed to obtain the selenium and silicate co-doped high-nickel cathode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 201mAh/g, and the capacity retention rate of 200 cycles is 87%.
Example 2
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.6Co0.2Al0.2Se0.01(SiO4)0.02O1.97。
The preparation method comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate, cobalt oxalate and sodium metaaluminate and a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a sodium hydroxide solution and ammonia water, controlling the temperature to be 75 ℃, stirring and reacting for 4 hours at the pH value of 12.5, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the positive electrode material obtained in the step (1) with lithium carbonate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.2:1, heating to 300 ℃ at the speed of 20 ℃/min in an oxygen atmosphere, sintering for 4h, continuing heating to 800 ℃, keeping the temperature for 10h, and cooling to room temperature along with the furnace after sintering is completed to obtain the selenium and silicate co-doped high-nickel positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 189mAh/g, and the capacity retention rate of 200 cycles is 85%.
Example 3
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.7Co0.1Mn0.1Al0.1Se0.05(SiO4)0.03O1.92。
The preparation method comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate, cobalt oxalate, manganese nitrate and sodium metaaluminate and a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a sodium hydroxide solution and ammonia water, controlling the temperature to be 60 ℃ and the pH value to be 11, carrying out stirring reaction for 10 hours, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the cathode material obtained in the step (1) with lithium hydroxide monohydrate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.05:1, heating to 500 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, sintering for 6h, continuing heating to 700 ℃ and keeping the temperature for 16h, and performing temperature programmed cooling to room temperature after sintering is completed to obtain the selenium and silicate co-doped high-nickel cathode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 194mAh/g, and the capacity retention rate of 200 cycles is 86%.
Example 4
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.7Mn0.15Al0.15Se0.03(SiO4)0.01O1.96。
The preparation method comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate, manganese nitrate and aluminum nitrate, a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a sodium hydroxide solution and ammonia water, controlling the temperature to be 55 ℃, stirring and reacting for 12 hours at the pH value of 11.5, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the cathode material obtained in the step (1) with lithium hydroxide monohydrate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.03:1, heating to 350 ℃ at the speed of 1 ℃/min in an oxygen atmosphere, sintering for 11h, continuing heating to 750 ℃ and keeping the temperature for 12h, and performing temperature programmed control and cooling to room temperature after sintering is completed to obtain the selenium and silicate co-doped high-nickel cathode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 195mAh/g, and the capacity retention rate of 200 cycles is 87%.
Example 5
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.5Co0.3Al0.2Se0.04(SiO4)0.02O1.94。
The preparation method comprises the following steps:
(1) preparing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate, cobalt oxalate and aluminum nitrate, a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a potassium hydroxide solution and ammonia water, controlling the temperature to be 70 ℃, stirring and reacting for 6 hours at the pH value of 10.5, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the cathode material obtained in the step (1) with lithium hydroxide monohydrate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.15:1, heating to 450 ℃ at the speed of 30 ℃/min in an oxygen atmosphere, sintering for 7h, continuing heating to 650 ℃ and preserving heat for 18h, and performing temperature programmed cooling to room temperature after sintering is completed to obtain the selenium and silicate co-doped high-nickel cathode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 186mAh/g, and the capacity retention rate of 200 cycles is 90%.
Example 6
The embodiment provides a selenium and silicate co-doped high-nickel cathode material, and the chemical formula of the cathode material is LiNi0.6Co0.4Se0.01(SiO4)0.02O1.97。
The preparation method comprises the following steps:
(1) mixing materials according to the content of each element in the chemical formula, adding a mixed solution of nickel nitrate and cobalt nitrate, a hydrazine hydrate solution of selenium and an ethanol solution of ethyl orthosilicate into a reaction vessel with a stirring device in a parallel flow manner, simultaneously adding a proper amount of a potassium hydroxide solution and ammonia water, controlling the temperature to be 50 ℃, carrying out stirring reaction for 14 hours at the pH value of 12, and carrying out solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the positive electrode material obtained in the step (1) with lithium carbonate, controlling the molar ratio of lithium element to metal element in the precursor to be 1.04:1, heating to 450 ℃ at the speed of 15 ℃/min in an oxygen atmosphere, sintering for 6h, continuing heating to 700 ℃ and keeping the temperature for 16h, and cooling to room temperature with the furnace after sintering is completed to obtain the selenium and silicate co-doped high-nickel positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 187mAh/g, and the capacity retention rate of 200 cycles is 86%.
Comparative example 1
The chemical formula of the positive electrode material provided by the comparative example is LiNi0.8Co0.1Mn0.1(SiO4)0.05O1.95The procedure and conditions were exactly the same as in example 1 except that the hydrazine hydrate solution without selenium was added in step (1) as compared with example 1.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 171mAh/g, and the capacity retention rate of 200 cycles is 63%.
Comparative example 2
The chemical formula of the positive electrode material provided by the comparative example is LiNi0.8Co0.1Mn0.1Se0.02O1.98Compared with the example 1, the steps and conditions are the same as the example 1 except that the ethanol solution of tetraethoxysilane is not added in the step (1).
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 177mAh/g, and the capacity retention rate of 200 cycles is 68%.
Comparative example 3
The chemical formula of the positive electrode material provided by the comparative example is LiNi0.8Co0.1Mn0.1O2The procedure and conditions were exactly the same as in example 1 except that the hydrazine hydrate solution without selenium and the ethanol solution of ethyl orthosilicate were not added in step (1) as compared with example 1.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2.5-4.2V and the current density of 0.1C, the first cyclic discharge specific capacity is 169mAh/g, and the capacity retention rate of 200 cycles is 59%.
From examples 1 to 6, the cathode material prepared by the invention has excellent electrochemical performance, the first cyclic discharge specific capacity is more than or equal to 185mAh/g, and the capacity retention rate of 200 cycles of circulation is more than or equal to 85% in a voltage window of 2.5 to 4.2V and a current density of 0.1C. As can be seen from comparative examples 1-3, compared with example 1, when selenium and silicate are not doped, the first cycle discharge specific capacity is only 169mAh/g, and the capacity retention rate of 200 cycles of the cycle is only 59%, which is far lower than the data in example 1; when only silicate radicals are doped (selenium is not doped), the electrochemical performance of the high-nickel positive electrode material is hardly improved; when only selenium is doped (no silicate is doped), the electrochemical performance of the high-nickel cathode material is improved to some extent, but the improvement range is not large. The selenium and the silicate have good synergistic effect and can jointly improve the electrochemical performance of the high-nickel cathode material.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (20)

1. The selenium and silicate co-doped high-nickel cathode material is characterized in that the cathode material is a selenium and silicate co-doped modified high-nickel cathode material with a chemical formula of LiNixM1-xSea(SiO4)bO2-a-bWherein M is at least one of Mn, Co or Al, x is more than or equal to 0.5 and less than 1, a is more than 0 and less than or equal to 0.05, and b is more than 0 and less than or equal to 0.05;
the preparation raw materials of the cathode material comprise a nickel source, an M source, a selenium source, a silicon source, a lithium source, a precipitator and a complexing agent, wherein the selenium source is a hydrazine hydrate solution of selenium.
2. The method of claim 1, wherein the method comprises the steps of:
(1) preparing materials according to the content of each element in the chemical formula, adding a nickel source, an M source, a selenium source, a silicon source, a precipitator and a complexing agent into a reaction container in a parallel flow manner, controlling the temperature and the pH value, stirring for reaction, and performing solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) and (2) mixing the precursor of the positive electrode material obtained in the step (1) with a lithium source, and performing heat treatment to obtain the selenium and silicate co-doped high-nickel positive electrode material.
3. The method of claim 2, wherein the reaction vessel of step (1) is provided with a stirring device.
4. The method of claim 2, wherein the nickel source of step (1) is nickel nitrate.
5. The method of claim 2, wherein M in step (1) is at least one of manganese, cobalt or aluminum, and accordingly, the manganese source is manganese chloride and/or manganese nitrate; the cobalt source is cobalt nitrate and/or cobalt oxalate; the aluminum source is aluminum nitrate and/or sodium metaaluminate.
6. The method of claim 2, wherein the selenium source of step (1) is a solution of selenium in hydrazine hydrate.
7. The method of claim 2, wherein the silicon source in step (1) is an ethanol solution of ethyl orthosilicate.
8. The method of claim 2, wherein the precipitating agent of step (1) is sodium hydroxide and/or potassium hydroxide.
9. The method of claim 2, wherein the complexing agent of step (1) is aqueous ammonia.
10. The method of claim 2, wherein the pH of the solution during the reaction of step (1) is from 10 to 12.5.
11. The process of claim 2, wherein the temperature of the reaction of step (1) is 45-75 ℃.
12. The method of claim 2, wherein the reaction time in step (1) is 4 to 16 hours.
13. The method according to claim 2, wherein after the solid-liquid separation in step (1), the obtained product is washed and dried to obtain the positive electrode material precursor.
14. The method of claim 2, wherein the lithium source of step (2) is lithium carbonate and/or lithium hydroxide monohydrate.
15. The method of claim 2, wherein the molar ratio of lithium element in the lithium source to metal element in the positive electrode material precursor in step (2) is (1-1.2): 1.
16. The method of claim 2, wherein the heat treatment of step (2) is performed in an oxygen atmosphere.
17. The method of claim 2, wherein the heat treatment of step (2) has a ramp rate of 1-30 ℃/min.
18. The method of claim 2, wherein said heat treatment of step (2) is performed in two stages, a first stage: sintering at the temperature of 300 ℃ and 500 ℃ for 4-12 h; and a second stage: the product in the first stage is heated to 600-800 ℃ and sintered for 10-20 h.
19. The method according to any one of claims 2-18, characterized in that the method comprises the steps of:
(1) preparing materials according to the content of each element in the chemical formula, adding a nickel source, an M source, a selenium source, a silicon source, a precipitator and a complexing agent into a reaction container with a stirring device in a parallel flow manner, controlling the temperature to be 45-75 ℃, the pH value to be 10-12.5, stirring and reacting for 4-16h, and performing solid-liquid separation after the reaction is finished to obtain a precursor of the anode material;
(2) mixing the precursor of the cathode material obtained in the step (1) with a lithium source, controlling the molar ratio of the lithium element in the lithium source to the metal element in the precursor to be (1-1.2):1, heating to 300-800 ℃ at the rate of 1-30 ℃/min under the oxygen atmosphere, sintering for 4-12h, then continuing heating to 600-800 ℃ and sintering for 10-20h, and cooling to obtain the selenium and silicate co-doped high-nickel cathode material.
20. The use of the selenium and silicate co-doped high nickel cathode material of claim 1 as a cathode material for a lithium ion battery.
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