CN115057485A - Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a non-metal boron-doped layered oxide sodium ion battery anode material and a preparation method and application thereof, wherein the chemical formula of the anode material is NaNi 0.5 Mn 0.5 B x O 2 (0≤x<0.1). The positive electrode material provided by the invention has long cycling stability, excellent rate capability and lower cost price, and is a sodium ion battery positive electrode material with development prospect; in addition, the cathode material provided by the invention is successfully induced into an O3/P2 two-phase composite structure after being doped with boron, and the interaction of the two phases is realizedMore excellent electrochemical performance is obtained.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a non-metal boron-doped layered oxide sodium ion battery positive electrode material with excellent electrochemical performance, and a preparation method and application thereof.
Background
With the continuous progress of the industrial revolution, the consumption of fossil energy is more and more, but due to the limited fossil energy reserves, if the continuous exploitation and use are carried out, the energy can be exhausted all the day, and the exploration of sustainable energy is particularly important under the severe condition. In the continuous research process, renewable energy sources such as wind energy, water energy and tidal energy gradually receive wide attention from the scientific community, and in view of the characteristics of cleanness, no pollution and the like, the renewable energy sources are limited by the defects of regionality, intermittency and the like of the energy sources, and are difficult to develop and apply on a large scale, so that a more sustainable, efficient and portable energy storage system needs to be explored and researched. Lithium ion batteries have received extensive attention due to their high electrochemical capacity and long cycling stability, and have been successfully commercialized in continuous research and research. However, the low reserve of lithium resources and the high price of lithium limit the long-term development of lithium ion batteries, and more suitable energy storage devices need to be explored, and in this case, the same main group of sodium ion batteries are considered to be the most promising alternatives to lithium ion batteries due to their wide reserve of sodium resources and their physicochemical properties similar to lithium. However, due to the larger radius of sodium ions, which leads to the collapse of the structure during electrochemical cycling, a more suitable positive electrode material needs to be found for use therein. The layered transition metal oxide material is considered to have a development prospect due to the characteristics of higher working voltage, electrochemical capacity and the like, but the rapid development step is limited by the complex phase transition process in the cycle process, so that a more appropriate method is needed for relevant modification to obtain a battery cathode material with higher performance.
Disclosure of Invention
In view of the above circumstances, the technical problem to be solved by the present invention is to provide a non-metal boron-doped layered oxide sodium ion battery positive electrode material and a preparation method thereof, and the positive electrode material provided by the present invention has the characteristics of good cycling stability, high rate performance, etc., and is simple in preparation process and high in yield.
The invention adopts the following technical scheme for realizing the purpose:
the inventionFirstly, a non-metal boron-doped layered oxide sodium ion battery anode material is disclosed, the chemical formula of which is NaNi 0.5 Mn 0.5 B x O 2 Wherein 0 is less than or equal to x<0.1。
The non-metal boron-doped layered oxide sodium ion battery positive electrode material can be prepared by a sol-gel method or a solid-phase synthesis method.
The method for preparing the non-metal boron-doped layered oxide sodium ion battery anode material by adopting the sol-gel method comprises the following steps:
step 11, dissolving a sodium source compound, a nickel source compound, a manganese source compound and a boron source compound in deionized water according to a molar ratio, adding a chelating agent, stirring until the mixture is uniformly mixed, and heating and volatilizing a solvent in a constant-temperature oil bath to obtain a precursor;
step 12, drying the precursor and then grinding to obtain precursor powder;
step 13, calcining the precursor powder in two steps to obtain the non-metal boron-doped layered oxide sodium ion battery anode material NaNi 0.5 Mn 0.5 B x O 2 。
The method for preparing the non-metal boron-doped layered oxide sodium ion battery anode material by adopting the solid-phase synthesis method comprises the following steps:
step 21, placing a sodium source compound, a nickel source compound, a manganese source compound and a boron source compound in a mortar according to a molar ratio, and grinding until the materials are fully mixed to obtain mixture powder;
step 22, tabletting the mixture powder by using a tablet machine to enable the contact between samples to be more compact, and obtaining a precursor sample;
step 23, calcining the precursor sample in two steps to obtain the non-metal boron-doped layered oxide sodium ion battery anode material NaNi 0.5 Mn 0.5 B x O 2 。
When a sol-gel method is employed: the sodium source compound is one or more of sodium acetate, sodium oxalate, sodium chloride, sodium nitrate and sodium citrate; the nickel source compound is one or more of nickel acetate, nickel oxalate, nickel nitrate, nickel sulfate and nickel chloride; the manganese source compound is one or more of manganese acetate, manganese oxalate, manganese nitrate, manganese sulfate and manganese chloride; the boron source compound is one or more of boron oxide, boric acid, sodium borohydride and boron fluoride; the chelating agent is one or more of oxalic acid, citric acid, tartaric acid or ethylenediamine tetraacetic acid.
When solid phase synthesis is used: the sodium source compound is one or more of sodium carbonate, sodium oxide, sodium acetate, sodium chloride, sodium nitrate and sodium citrate; the nickel source compound is one or more of nickel carbonate, nickel oxide, nickel acetate, nickel nitrate, nickel sulfate and nickel chloride; the manganese source compound is one or more of manganese carbonate, manganese oxide, manganese acetate, manganese nitrate, manganese sulfate and manganese chloride; the boron source compound is one or more of boron oxide, boric acid, sodium borohydride and boron fluoride.
Preferably, in step 11, the molar ratio of the total molar amount of the sodium source compound, the nickel source compound, the manganese source compound and the boron source compound to the chelating agent is 1: 2.
Preferably, the two calcining steps of step 13 and step 23 are performed in an air atmosphere, and are divided into a first pre-calcining step and a second high-temperature calcining step; the temperature rise temperature of the first-step pre-calcination is 350-600 ℃, the temperature rise rate is 2-10 ℃/min, and the temperature is kept for 4-10 h; and in the second step, the temperature rise temperature of the high-temperature calcination is 800-1000 ℃, the temperature rise rate is 2-10 ℃/min, the temperature is kept for 10-24 h, and the temperature is reduced to the room temperature after the temperature is kept.
The invention also discloses a sodium ion battery positive plate which is prepared from the positive material, a conductive additive, a binder and a relevant solvent, wherein the positive material is selected from the non-metal boron-doped layered oxide sodium ion battery positive material.
The invention also discloses a sodium ion battery which is composed of the prepared positive plate, the diaphragm, the organic electrolyte and the negative metal sodium and can be applied to various energy storage devices, such as electric automobiles, solar power generation, wind power generation, smart grid peak regulation, distributed power stations or communication bases and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a high-performance layered oxide sodium ion battery anode material with a chemical formula of NaNi 0.5 Mn 0.5 B x O 2 Wherein 0 is less than or equal to x<0.1. The positive electrode material provided by the invention has long cycling stability, excellent rate capability and lower cost price, and is a sodium ion battery positive electrode material with development prospect; meanwhile, the cathode material provided by the invention is successfully induced into an O3/P2 two-phase composite structure after being doped with boron, and more excellent electrochemical performance is obtained through the interaction of the two phases. In addition, the anode material provided by the invention has the advantages of simple synthesis method, obvious performance effect and easiness in mass production.
Drawings
FIG. 1 is an SEM image of the target product obtained in example 1.
FIG. 2 is the XRD spectrum of the target product obtained in example 1.
FIG. 3 is a charge-discharge curve of the target product obtained in example 1 at a magnification of 0.1C.
FIG. 4 is a chart of the cycle stability of the target product obtained in example 1 at a current density of 1C.
FIG. 5 is a graph of rate capability of the target product obtained in example 1 in the range of 0.1C-5C.
FIG. 6 is a cycle stability spectrum of the target product obtained in example 1 at a current density of 5C.
FIG. 7 is the XRD spectrum of the target product obtained in example 2.
FIG. 8 is a graph of the cycling stability of the target product of example 2 at a current density of 1C.
FIG. 9 is the XRD spectrum of the target product obtained in example 3.
FIG. 10 is a graph of the cycling stability of the target product of example 3 at a current density of 1C.
FIG. 11 is the XRD spectrum of the target product obtained in example 4.
FIG. 12 is a graph of the cycling stability of the target product of example 4 at 1C current density.
FIG. 13 is a charge/discharge curve of the objective product obtained in example 5 at a magnification of 0.1C.
Detailed Description
The invention provides a non-metal boron-doped layered oxide sodium ion battery anode material with long cycle stability and excellent rate performance, and the chemical formula is NaNi 0.5 Mn 0.5 B x O 2 Wherein 0 is less than or equal to x<0.1. The positive electrode material of the sodium-ion battery provided by the invention is blocky.
In some embodiments of the invention, the positive electrode material of the sodium-ion battery is NaNi 0.5 Mn 0.5 B 0.02 O 2 The best overall performance and cycling stability, 1C (150 mAg ═ 1C) -1 ) The capacity retention rate of 200 cycles under the current density is 90.5%, and the original capacity of 62.0% can be still maintained under the current density of large current 5C in the rate performance test, so that the material is a sodium ion battery anode material with a good development prospect. .
The invention also successfully prepares a sodium ion battery positive plate, which is prepared from a positive active material, a conductive additive, a binder and a solvent, wherein: the positive active material is selected from the synthesized boron-doped layered oxide sodium ion battery positive material; the conductive additive is selected from one or more of carbon black, Super-P and Ketjen black; the binder is selected from one or more of polyacrylic acid, polyvinylidene fluoride, sodium carboxymethylcellulose and sodium alginate; the solvent is selected from one or more of N-methyl pyrrolidone or deionized water.
The invention also provides a preparation method of the sodium ion battery positive plate, which is to mix the positive material, the conductive additive, the binder and the solvent, and then prepare the battery positive plate through smearing and drying.
The specific methods of mixing, smearing and drying used herein are general preparative methods according to methods well known to those skilled in the art.
The invention also provides a sodium ion battery, which consists of a positive plate, a diaphragm, electrolyte and negative metal sodium, wherein: the positive plate adopts the sodium ion battery positive plate. The electrolyte is carbonate electrolyte, the concentration of the solution is 0.5-2M, and 1M is preferred; the solvent in the electrolyte is selected from one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and fluorinated ethylene carbonate, and is preferably a mixed solvent of propylene carbonate and fluorinated ethylene carbonate; the solute in the electrolyte is selected from one or more of sodium perchlorate, sodium hexafluorophosphate and sodium bistrifluoromethylsulfonyl imide, and is preferably sodium perchlorate. The separator is preferably glass fiber.
The invention also provides application of the sodium ion battery in large-scale energy storage devices such as electric vehicles, solar power generation, wind power generation, smart grid peak shaving, distributed power stations or communication bases.
The invention has the following advantages:
(1) the chemical formula of the synthesized nonmetal boron-doped blocky layered oxide sodium ion battery anode material is NaNi 0.5 Mn 0.5 B x O 2 (0≤x<0.1), has promoted the long-term development of the material system of the sodium ion battery.
(2) NaNi of the invention 0.5 Mn 0.5 B x O 2 (0≤x<0.1) the cathode material has long cycling stability, excellent rate capability and low cost, and is a sodium ion battery cathode material with development prospect.
(3) NaNi which is the most preferred in the present invention 0.5 Mn 0.5 B 0.02 O 2 The cycle stability of the positive electrode material is best at 1C (150 mAg ═ 1C) -1 ) The capacity retention rate of 200 cycles under the current density is 90.5%, the rate capability is very good, the 5C rate can still maintain 62.0% of the original capacity, and the lithium ion battery is an ideal anode material for preparing a sodium ion battery energy storage device.
(4) Compared with the material which is not doped with non-metallic boron, the anode material synthesized by the method has better comprehensive performance.
In order to further understand the present invention, the following description is made with reference to specific examples to illustrate the high performance layered oxide sodium ion battery positive electrode material provided by the present invention, and the preparation method and application thereof, and the protection scope of the present invention is not limited by the following examples.
Example 1
Step 1, preparing NaNi by a sol-gel method 0.5 Mn 0.5 B 0.02 O 2 Positive electrode material
Dissolving sodium acetate, nickel acetate, manganese acetate and boric acid in deionized water according to the molar ratio in the chemical formula, adding citric acid (the molar ratio of the total molar amount of the sodium acetate, the nickel acetate, the manganese acetate and the boric acid to the citric acid is 1:2), and stirring until the mixture is uniformly mixed. And then putting the solution into an oil bath with the constant temperature of 70 ℃, and continuously stirring until the solution is completely evaporated to dryness to form a precursor. And transferring the precursor to a drying oven at 150 ℃ for drying for 6h, and after cooling to room temperature, putting the precursor into a mortar for grinding until precursor powder is formed.
And (3) placing the precursor powder in a muffle furnace to carry out two-step calcination under air atmosphere: the temperature rise temperature of the first step of precalcination is 450 ℃, the temperature rise rate is 2 ℃/min, and the temperature is kept for 6 h; the temperature rise temperature of the second step of high-temperature calcination is 900 ℃, the temperature rise rate is 2 ℃/min, the temperature is kept for 15h, and the temperature is reduced to the room temperature after the temperature is kept, so that the target product NaNi is obtained 0.5 Mn 0.5 B 0.02 O 2 。
Step 2, preparing the positive plate of the sodium-ion battery
Mixing the NaNi 0.5 Mn 0.5 B 0.02 O 2 Mixing the positive electrode material with Super P and polyvinylidene fluoride binder (PVDF) according to the mass ratio of 7:2:1, adding a proper amount of N-methyl pyrrolidone as a solvent, pulping by a mixer, smearing, drying and the like to obtain the NaNi-containing composite material 0.5 Mn 0.5 B 0.02 O 2 The positive plate of the sodium ion battery is made of a positive material.
Step 3, assembling to synthesize a product NaNi 0.5 Mn 0.5 B 0.02 O 2 A sodium ion battery which is a positive electrode.
Assembling the prepared sodium ion battery positive plate and the metal sodium negative electrode into a sodium ion battery, wherein GF/F is a battery diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO) 4 in PC)。
Fig. 1 is an SEM picture of the cathode material prepared in example 1, from which it can be seen that the material is a block-shaped structure.
Fig. 2 is an XRD picture of the cathode material obtained in example 1, which shows that the synthesized layered oxide cathode material has a two-phase structure, i.e., O3/P2 composite phase, and mainly contains O3 phase.
Fig. 3 shows the positive electrode material obtained in example 1 at 0.1C (1C 150 mAg) -1 ) The charging and discharging curve under the current density can be seen from the figure, the synthesized material has 115.4mAh g in the sodium ion battery -1 Higher specific discharge capacity.
Fig. 4 is a cycle stability curve of the sodium-ion battery assembled by the positive electrode material obtained in example 1 at a rate of 1C, and it can be seen from the graph that after 200 cycles, the capacity retention rate can still reach 90.5%.
Fig. 5 is a graph showing the rate performance of the positive electrode material obtained in example 1 in the range of 0.1C to 5C, and it can be seen from the graph that all the positive electrode materials from 0.1C to 5C exhibit relatively good electrochemical capacity, and the initial capacity of 62.0% can be maintained at the rate of 5C, and excellent rate performance is shown.
Fig. 6 is a graph showing the cycle stability at 5C current density of the sodium-ion battery assembled with the cathode material obtained in example 1, and shows that there is no significant capacity fade after 700 cycles.
Example 2
The preparation method is the same as that of example 1, and the synthesized compound is NaNi 0.5 Mn 0.5 B 0.01 O 2 The anode material of (1) sodium acetate, nickel acetate, manganese acetate and boric acid are taken according to the molar ratio in the chemical formula.
FIG. 7 shows NaNi obtained in example 2 0.5 Mn 0.5 B 0.01 O 2 The XRD pattern of the material shows that the synthesized layered oxide cathode material has better crystallinity, has an O3/P2 phase structure and takes an O3 phase as a main body.
FIG. 8 shows NaNi obtained in example 2 0.5 Mn 0.5 B 0.01 O 2 Sodium ion battery assembled with positive electrode material at 1C (1C 150 mAg) -1 ) The cycle stability chart under the current density shows that after 200 cycles, the capacity is only 61.5mAh g -1 Is reserved.
Example 3
The preparation method is the same as that of example 1, and the synthesized compound is NaNi 0.5 Mn 0.5 B 0.04 O 2 The anode material of (1) sodium acetate, nickel acetate, manganese acetate and boric acid are taken according to the molar ratio in the chemical formula.
FIG. 9 shows NaNi obtained in example 3 0.5 Mn 0.5 B 0.04 O 2 The XRD pattern of the material shows that the synthesized layered oxide cathode material has better crystallinity, has an O3/P2 phase structure and takes an O3 phase as a main body.
FIG. 10 shows NaNi obtained in example 3 0.5 Mn 0.5 B 0.04 O 2 Sodium ion battery assembled with positive electrode material at 1C (1C 150 mAg) -1 ) The cycle stability under current density is shown in the graph, and after 200 cycles, the capacity still remains 83.2mAh g -1 。
Example 4
The preparation method is the same as that of example 1, and the synthesized compound is NaNi 0.5 Mn 0.5 B 0.06 O 2 The anode material of (1) sodium acetate, nickel acetate, manganese acetate and boric acid are taken according to the molar ratio in the chemical formula.
FIG. 11 shows NaNi obtained in example 4 0.5 Mn 0.5 B 0.06 O 2 The XRD pattern of the material shows that the synthesized layered oxide cathode material has better crystallinity, has an O3/P2 phase structure and takes an O3 phase as a main body.
FIG. 12 shows NaNi obtained in example 4 0.5 Mn 0.5 B 0.06 O 2 Sodium ion battery assembled by positive electrode material at 1C (1C ═ 150 mAg) -1 ) The cycle stability under current density is shown in the graph, and after 200 cycles, the capacity still remains 73.8mAh g -1 。
Example 5
Step 1, solid phase synthesis method preparationNaNi 0.5 Mn 0.5 B 0.02 O 2 Positive electrode material
Sodium carbonate, nickel oxide, manganese oxide and boron oxide are mixed according to the chemical formula NaNi 0.5 Mn 0.5 B 0.02 O 2 The molar ratio of (1) is put in a mortar, and the mixture is ground until the mixture is fully mixed to obtain mixture powder;
tabletting the mixture powder by using a tablet machine to ensure that the contact between samples is tighter, and obtaining a precursor sample;
the precursor sample was subjected to two-step calcination: the temperature rise temperature of the first step of precalcination is 450 ℃, the temperature rise rate is 2 ℃/min, and the temperature is kept for 6 h; in the second step, the temperature rise temperature of the high-temperature calcination is 900 ℃, the temperature rise rate is 2 ℃/min, the temperature is kept for 15h, and the temperature is reduced to the room temperature after the temperature is kept, so that the target product NaNi is obtained 0.5 Mn 0.5 B 0.02 O 2 。
Step 2, preparing the positive plate of the sodium-ion battery
Mixing the NaNi prepared above 0.5 Mn 0.5 B 0.02 O 2 Mixing the positive electrode material with Super P and polyvinylidene fluoride binder (PVDF) according to the mass ratio of 7:2:1, adding a proper amount of N-methyl pyrrolidone as a solvent, pulping by a mixer, smearing, drying and the like to obtain the NaNi-containing composite material 0.5 Mn 0.5 B 0.02 O 2 The positive plate of the sodium ion battery is made of a positive material.
Step 3, assembling with NaNi 0.5 Mn 0.5 B 0.02 O 2 The material is a sodium ion battery of the positive pole.
Assembling the prepared positive plate and metal sodium negative electrode of the sodium-ion battery into the sodium-ion battery, wherein GF/F is a battery diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO) 4 in PC)。
Fig. 13 shows the positive electrode material of example 5 assembled with a sodium ion battery at 0.1C (1C-150 mAg) -1 ) The charging and discharging curve under the current density can release 109.9mAh g in the initial circulation process as can be seen from the figure -1 The electrochemical capacity of (c).
The foregoing is only a preferred implementation of the invention, and it should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the invention, and should be considered as the scope of the invention.
Claims (7)
1. A non-metal boron-doped layered oxide sodium ion battery positive electrode material is characterized in that: the chemical formula of the positive electrode material of the sodium-ion battery is NaNi 0.5 Mn 0.5 B x O 2 Wherein 0 is less than or equal to x<0.1。
2. A method for preparing the positive electrode material of the non-metal boron-doped layered oxide sodium ion battery of claim 1, which is characterized in that: is prepared by a sol-gel method or a solid-phase synthesis method.
3. The production method according to claim 2, characterized in that:
the method for preparing the non-metal boron-doped layered oxide sodium ion battery anode material by adopting the sol-gel method comprises the following steps:
step 11, dissolving a sodium source compound, a nickel source compound, a manganese source compound and a boron source compound in deionized water according to a molar ratio, adding a chelating agent, stirring until the mixture is uniformly mixed, and heating and volatilizing a solvent in a constant-temperature oil bath to obtain a precursor;
step 12, drying the precursor and then grinding to obtain precursor powder;
step 13, calcining the precursor powder in two steps to obtain the non-metal boron-doped layered oxide sodium ion battery anode material NaNi 0.5 Mn 0.5 B x O 2 ；
The method for preparing the non-metal boron-doped layered oxide sodium ion battery anode material by adopting the solid-phase synthesis method comprises the following steps:
step 21, placing a sodium source compound, a nickel source compound, a manganese source compound and a boron source compound in a mortar according to a molar ratio, and grinding until the materials are fully mixed to obtain mixture powder;
step 22, tabletting the mixture powder by using a tablet machine to ensure that the contact between samples is more compact and a precursor sample is obtained;
step 23, calcining the precursor sample in two steps to obtain the non-metal boron-doped layered oxide sodium ion battery anode material NaNi 0.5 Mn 0.5 B x O 2 。
4. The production method according to claim 3, characterized in that:
when a sol-gel method is employed: the sodium source compound is one or more of sodium acetate, sodium oxalate, sodium chloride, sodium nitrate and sodium citrate; the nickel source compound is one or more of nickel acetate, nickel oxalate, nickel nitrate, nickel sulfate and nickel chloride; the manganese source compound is one or more of manganese acetate, manganese oxalate, manganese nitrate, manganese sulfate and manganese chloride; the boron source compound is one or more of boron oxide, boric acid, sodium borohydride and boron fluoride; the chelating agent is one or more of oxalic acid, citric acid, tartaric acid or ethylenediamine tetraacetic acid;
when solid phase synthesis is used: the sodium source compound is one or more of sodium carbonate, sodium oxide, sodium acetate, sodium chloride, sodium nitrate and sodium citrate; the nickel source compound is one or more of nickel carbonate, nickel oxide, nickel acetate, nickel nitrate, nickel sulfate and nickel chloride; the manganese source compound is one or more of manganese carbonate, manganese oxide, manganese acetate, manganese nitrate, manganese sulfate and manganese chloride; the boron source compound is one or more of boron oxide, boric acid, sodium borohydride and boron fluoride.
5. The production method according to claim 3, characterized in that: the two-step calcination of the step 13 and the step 23 is carried out in an air atmosphere and is divided into a first-step pre-calcination and a second-step high-temperature calcination; the temperature rise temperature of the first-step pre-calcination is 350-600 ℃, the temperature rise rate is 2-10 ℃/min, and the temperature is kept for 4-10 h; and in the second step, the temperature rise temperature of the high-temperature calcination is 800-1000 ℃, the temperature rise rate is 2-10 ℃/min, the heat preservation is carried out for 10-24 h, and the temperature is reduced to the room temperature after the heat preservation is finished.
6. A positive plate of a sodium ion battery is prepared from a positive material, a conductive additive, a binder and a solvent, and is characterized in that: the positive electrode material is selected from the non-metal boron-doped layered oxide sodium ion battery positive electrode material of claim 1.
7. The utility model provides a sodium ion battery comprises positive plate, diaphragm, organic electrolyte and negative pole metallic sodium, its characterized in that: the positive plate is the sodium-ion battery positive plate according to claim 6.
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