CN111362269A - Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material - Google Patents
Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material Download PDFInfo
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Abstract
The invention relates to the field of lithium ion batteries, and on one hand, discloses a preparation method of an SEI (solid electrolyte interphase) film of a lithium ion battery cathode, wherein the SEI film is obtained by pre-lithiating a silicon monoxide cathode material and is Li on SiOx @ Si surface2SiO3(ii) a The preparation method has the advantages of safe experiment, convenient operation, low cost and easy batch production. On the other hand, the negative electrode material of the lithium ion battery is SiOx @ Si/Li2SiO3a/C composite material. The composite material not only exerts the characteristic of high silicon material capacity, but also overcomes the defects of low first coulombic efficiency and poor cycle stability of a high-capacity silicon negative electrode material; the composite silicon-based electrode material is applied to the lithium ion battery, so that the first coulombic efficiency and the cycling stability of the battery can be effectively improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of an SEI (solid electrolyte interphase) film of a lithium ion battery cathode, a lithium ion battery cathode material and application thereof.
Background
With the continuous expansion of the electric vehicle market, the demand for high-performance lithium ions is also rapidly increasing. In the aspect of negative electrode materials, the theoretical capacity of the graphite material widely applied at present is 372mAh/g, and the demand of a high-capacity lithium ion battery is difficult to meet. Silicon-based materials such as Si and SiO2The lithium ion battery has the advantages of high specific capacity, rich reserves, low lithium removal potential and the like, and is widely concerned. However, when a silicon-based material is used for an electrode material, there is a great volume change during charge and discharge, and the active particles are pulverized during cycling due to a great stress, thereby causing deterioration in contact between the electrode materials and between the material and a substrate, resulting in rapid reduction in battery capacity. Moreover, the stability of an SEI film formed by the reaction of the silicon-based material and the electrolyte is poor, and along with the volume change of silicon, a fresh interface continuously appears on the surface of the silicon-based material and the SEI film is repeatedly formed, so that the electrolyte and lithium ions are continuously consumed, and the coulombic efficiency of the electrode in the first and subsequent circulation processes is reduced. The silicon-based material is subjected to pre-lithiation treatment, so that the first time can be improvedThe coulombic efficiency can also reduce the irreversible consumption of a lithium source, thereby effectively improving the capacity and the electrochemical performance of the battery. On the basis of the pre-lithiation treatment, the silicon material is coated with carbon, so that the cycle performance of the silicon material can be further improved.
Patent CN110178252A adopts a short circuit method to pre-lithiate a silicon-based material, and under a pressurized condition, the silicon-based material and lithium metal are combined into a short circuit galvanic cell to achieve the purpose of pre-lithiation. Patent CN105845894B adopts an electrochemical method to perform pre-lithiation on a silicon-based material, and can perform more controllable pre-lithiation on the silicon-based material by controlling current. Patent CN107394161A discloses a carbon-coated layer formed by chemical vapor deposition after pre-lithiation of a silicon-based material mixed with a lithium salt.
The methods of the patents CN110178252A and CN105845894B both use metal lithium, so that the pre-lithiation process has larger potential safety hazard, is not beneficial to being used in large-scale production, and has higher requirements on the pre-lithiation process and environment; meanwhile, most of the surface pre-lithiation layers obtained by the pre-lithiation method are lithium silicon alloy or lithium silicate, and are compact and brittle layers, poor in toughness and lack of buffer layers for bearing volume expansion of internal silicon-based materials, so that the cycling stability of the materials is not facilitated. The CN107394161A patent adopts CVD method to coat the carbon layer, which is high in cost.
Therefore, the prior art has the following problems:
1. in the prior pre-lithiation method of the silicon-based material, metal lithium is mostly adopted as a lithium source, so that the method has larger potential safety hazard;
2. the pre-lithiation layer on the surface of the pre-lithiated silicon-based material is mostly compact and brittle, so that the cyclic stability of the silicon-based material is not facilitated, and a buffer layer for bearing the volume expansion of the silicon-based material needs to be further constructed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of an SEI (solid electrolyte interphase) film of a lithium ion battery negative electrode, a lithium ion negative electrode material and application thereof. Specifically, a method for preparing an artificial SEI film by pre-lithiating a silicon oxide negative electrode material, and the artificial SEI film is applied to a lithium ion battery negative electrode material, wherein the prepared material is the silicon oxide negative electrode materialSilicon @ silicon/lithium silicate/carbon (SiO @ Si/Li)2SiO3The composite material not only exerts the characteristic of high silicon material capacity, but also overcomes the defects of low first coulombic efficiency and poor cycle stability of a high-capacity silicon negative electrode material. The composite silicon-based electrode material is applied to the lithium ion battery, so that the first coulombic efficiency and the cycling stability of the battery can be effectively improved.
In order to achieve the purpose, the technical measures adopted by the invention comprise:
the invention provides a preparation method of an SEI film of a negative electrode of a lithium ion battery, which uses inorganic salt lithium carbonate to pre-lithiate a silicon oxide negative electrode material to prepare an artificial SEI film and comprises the following steps:
step one, ultrasonically dispersing silicon monoxide in deionized water to form slurry, sanding the slurry in a nitrogen atmosphere for 0.5-2h by using a sand mill, and then collecting nano SiOx powder by spray drying;
placing the SiOx powder in a tubular furnace, and carrying out high-temperature heat treatment in an argon atmosphere to obtain a composite material in which nano Si microcrystals are uniformly embedded in a SiOx matrix, namely the SiOx @ Si composite material;
and step three, carrying out prelithiation on the composite material by using lithium carbonate: ultrasonically mixing the SiOx @ Si composite material obtained in the step two with lithium carbonate and polypropylene alcohol in water at the temperature of 80-100 ℃ to form slurry, placing the powder collected after spray drying in a tubular furnace, and heating for 5-7h at the temperature of 800-2SiO3。
Further, the particle diameter D50 of the nano-silica powder obtained by sand grinding in the step one is 100-500 nm.
Further, D50 is preferably 100-300 nm.
Further, the mass ratio of SiOx @ Si, lithium carbonate and polypropylene alcohol in the third step is 20:2: 1.
Further, the high-temperature heat treatment temperature in the second step is 800-1200 ℃, and the heat treatment time is 2-4 h.
Further, the spray drying mode used in step one and step three is open spray drying.
Further, the air inlet temperature during the open type spray drying is 150-300 ℃; the air outlet temperature is 60-120 ℃.
Further, the air inlet temperature is preferably 200-220 ℃; the air outlet temperature is preferably 80-100 ℃.
Furthermore, after the materials are placed in the tubular furnace in the third step, corresponding gas is used for replacing the materials in the furnace, and the replacement time is 1-2 hours.
The second aspect of the invention provides a lithium ion battery cathode material, which is SiOx @ Si/Li2SiO3a/C composite material.
Further, SiOx @ Si/Li obtained by the preparation method of the SEI film for the negative electrode of the lithium ion battery2SiO3Ultrasonically mixing the composite material and an organic carbon source through an aqueous solution, placing the powder collected after spray drying into a tubular furnace, and treating for 5-7h at the temperature of 600-800 ℃ in the atmosphere of hydrogen-argon mixed gas to obtain the lithium ion battery cathode material.
Further, the spray drying mode used is open spray drying.
Further, the air inlet temperature during the open type spray drying is 150-300 ℃; the air outlet temperature is 60-120 ℃.
Further, the organic carbon source is one of phenolic resin, glucose, vitamin C and sucrose.
Further, SiOx @ Si/Li2SiO3The mass ratio of the composite material to the organic carbon is 2-6: 1.
the third aspect of the invention is to provide the application of the lithium ion battery negative electrode material in the preparation of a lithium ion battery.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that:
1. the prelithiation process in the preparation of the negative electrode SEI of the lithium ion battery adopts lithium carbonate as lithium salt instead of metal lithium, and has the advantages of safe experiment, convenient operation, low cost and easy batch production;
2. in the process of preparing the SEI film of the lithium ion battery cathode, nano silicon crystal is generated in the SiO substrate, so that the capacity of the material is improved;
3. meanwhile, an artificial SEI film is prepared on the surface of the silicon monoxide powder through simple solid-phase reaction, and the inner layer of the SEI film is Li with compact structure and good electronic insulation2SiO3The carbon layer obtained by carbonizing the asphalt on the outer layer is used as a buffer layer for bearing the volume expansion of the silicon-based material in the inner part, so that the material can be kept stable in structure, and the circulation stability of the material is remarkably improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1
The present embodiment provides a SiOx @ Si/Li2SiO3The preparation method of the/C composite material comprises the following steps:
ultrasonically dispersing the silicon oxide in deionized water to form slurry, sanding the slurry for 1h in inert atmosphere by a sand mill, and then collecting the nano SiOx powder by spray drying. Placing 5g of SiOx powder in a tubular furnace, and carrying out heat treatment for 3h at 800 ℃ in an argon atmosphere to obtain a composite material in which nano Si microcrystals are uniformly embedded in a SiOx matrix, so as to obtain a SiOx @ Si composite material; the SiOx @ Si composite material and Li2CO3Ultrasonically mixing polypropylene glycol in water of 90 ℃ to form slurry, spray-drying the slurry, putting the collected powder in a tubular furnace, heating the powder for 6 hours at 1000 ℃ in a nitrogen atmosphere, and preparing the SiOx @ Si/Li2SiO3Wherein the mass ratio of SiOx @ Si to lithium carbonate to polypropylene alcohol is 20:2: 1. Finally will makeThe prepared composite material and vitamin C are uniformly mixed by a stirrer according to the mass ratio of 2:1, and then the mixture is placed in a tubular furnace and treated for 6 hours at the temperature of 750 ℃ in the atmosphere of hydrogen and argon. Preparation of SiOx @ Si/Li2SiO3a/C composite material.
Electrochemical tests were carried out on the prepared composite material and lithium sheets to form button cells, and the results are shown in table 1.
Example 2
The present embodiment provides a SiOx @ Si/Li2SiO3The preparation method of the/C composite material comprises the following steps:
ultrasonically dispersing the silicon oxide in deionized water to form slurry, sanding the slurry for 1h in inert atmosphere by a sand mill, and then collecting the nano SiOx powder by spray drying. Placing 5g of SiOx powder in a tubular furnace, and carrying out heat treatment for 3h at 1000 ℃ in an argon atmosphere to obtain a composite material in which nano Si microcrystals are uniformly embedded in a SiOx matrix, so as to obtain a SiOx @ Si composite material; the SiOx @ Si composite material and Li2CO3Ultrasonically mixing polypropylene glycol in water of 90 ℃ to form slurry, spray-drying the slurry, putting the collected powder in a tubular furnace, heating the powder for 6 hours at 1000 ℃ in a nitrogen atmosphere, and preparing the SiOx @ Si/Li2SiO3Wherein the mass ratio of SiOx @ Si to lithium carbonate to polypropylene alcohol is 20:2: 1. And finally, uniformly mixing the prepared composite material and vitamin C in a mass ratio of 2:1 by a stirrer, placing the mixture in a tubular furnace, and treating for 6 hours at the temperature of 750 ℃ in a hydrogen-argon mixed gas atmosphere. Preparation of SiOx @ Si/Li2SiO3a/C composite material.
Electrochemical tests were carried out on the prepared composite material and lithium sheets to form button cells, and the results are shown in table 1.
Example 3
The present embodiment provides a SiOx @ Si/Li2SiO3The preparation method of the/C composite material comprises the following steps:
ultrasonically dispersing the silicon oxide in deionized water to form slurry, sanding the slurry for 1h in inert atmosphere by a sand mill, and then collecting the nano SiOx powder by spray drying. Taking 5g SiOx powder and placing the powder in a tube furnace, and carrying out heat treatment for 3h at 1200 ℃ in argon atmosphere to obtain SiOx matrixUniformly embedding the composite material of the nano Si microcrystal to obtain the SiOx @ Si composite material; the SiOx @ Si composite material and Li2CO3Ultrasonically mixing polypropylene glycol in water of 90 ℃ to form slurry, spray-drying the slurry, putting the collected powder in a tubular furnace, heating the powder for 6 hours at 1000 ℃ in a nitrogen atmosphere, and preparing the SiOx @ Si/Li2SiO3Wherein the mass ratio of SiOx @ Si to lithium carbonate to polypropylene alcohol is 20:2: 1. And finally, uniformly mixing the prepared composite material and vitamin C in a mass ratio of 2:1 by a stirrer, placing the mixture in a tubular furnace, and treating for 6 hours at the temperature of 750 ℃ in a hydrogen-argon mixed gas atmosphere. Preparation of SiOx @ Si/Li2SiO3a/C composite material.
Electrochemical tests were carried out on the prepared composite material and lithium sheets to form button cells, and the results are shown in table 1.
Example 4
The present embodiment provides a SiOx @ Si/Li2SiO3The preparation method of the/C composite material comprises the following steps:
SiOx @ Si/Li preparation according to example two2SiO3A composite material. And then uniformly mixing the prepared composite material and vitamin C in a mass ratio of 4:1 by a stirrer, placing the mixture in a tube furnace, and treating for 6 hours at 750 ℃ in a hydrogen-argon mixed gas atmosphere. The SiOx @ Si/Li2SiO3/C composite material is prepared.
Electrochemical tests were carried out on the prepared composite material and lithium sheets to form button cells, and the results are shown in table 1.
Example 5
The present embodiment provides a SiOx @ Si/Li2SiO3The preparation method of the/C composite material comprises the following steps:
SiOx @ Si/Li preparation according to example two2SiO3A composite material. And then uniformly mixing the prepared composite material and vitamin C in a mass ratio of 6:1 by a stirrer, placing the mixture in a tube furnace, and treating for 6 hours at 750 ℃ in a hydrogen-argon mixed gas atmosphere. Preparation of SiOx @ Si/Li2SiO3a/C composite material.
Electrochemical tests were carried out on the prepared composite material and lithium sheets to form button cells, and the results are shown in table 1.
Example 6
The present embodiment provides a SiOx @ Si/Li2SiO3The composite material is prepared by the following steps:
SiOx @ Si/Li preparation according to example two2SiO3The prepared composite material and a lithium sheet form a button cell for electrochemical test, and a blue test system is utilized to test the charge-discharge curve of the button cell, and the result is shown in table 1.
Comparative example 1
Ultrasonically dispersing the silicon oxide in deionized water to form slurry, sanding the slurry for 1h in inert atmosphere by a sand mill, and then collecting the nano SiOx powder by spray drying.
Electrochemical tests are carried out on the button cell consisting of the prepared nano SiOx and the lithium sheet, and the results are shown in Table 1.
TABLE 1 comparison of experimental data for CR2032 button cell
According to the results of examples 1-3, the capacity and the cycle capacity retention rate of the sample treated at 1000 ℃ are best, and the silicon microcrystal generated by the reaction at 800 ℃ is less than 1000 ℃ and the capacity ratio is slightly lower; at 1200 ℃, the silicon microcrystal can further react to form SiO with poor electrochemical activity2The sample performance is rather degraded. Examples 2, 4, 5, and 6 study the influence of the carbon source addition ratio, and the results show that the carbon source addition amount under the conditions of example 4 is most suitable, the first release capacity, the first effect, and the 50-cycle capacity retention rate are all better, and compared with example 6, the cycle performance of the carbon source addition sample is significantly improved; compared with the comparative example, the performance of all the treated samples is obviously improved.
It can be seen from the above examples that, compared to the comparative examples, the artificial SEI film is prepared on the surface of the silicon monoxide powder by a simple solid-phase reaction and applied to the lithium ion battery, which can improve the first coulombic efficiency and the cycle stability.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. It will be appreciated by those skilled in the art that any equivalent modifications and substitutions are within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of an SEI film of a negative electrode of a lithium ion battery is characterized in that lithium carbonate is used for pre-lithiating a silicon oxide negative electrode material to prepare the SEI film, and comprises the following steps:
step one, ultrasonically dispersing silicon monoxide in deionized water to form slurry, sanding the slurry in a nitrogen atmosphere for 0.5-2h by using a sand mill, and then collecting nano SiOx powder by spray drying;
placing the SiOx powder in a tubular furnace, and carrying out high-temperature heat treatment in an argon atmosphere to obtain a composite material in which nano Si microcrystals are uniformly embedded in a SiOx matrix, namely the SiOx @ Si composite material;
step three, ultrasonically mixing the SiOx @ Si composite material obtained in the step two with lithium carbonate and polypropylene alcohol in water at the temperature of 80-100 ℃ to form slurry, after spray drying, placing the collected powder in a tube furnace, heating for 5-7h at the temperature of 800-2SiO3A composite material.
2. The method for preparing the SEI film of the lithium ion battery cathode according to claim 1, wherein the grain diameter D50 of the nano-silica powder obtained by sand milling in the step one is 100-500 nm.
3. The method for preparing the SEI film for the negative electrode of the lithium ion battery as claimed in claim 1, wherein the temperature of the high temperature heat treatment in the second step is 800-1200 ℃ and the time is 2-4 h.
4. The method for preparing the SEI film of the lithium ion battery cathode is characterized in that the mass ratio of SiOx @ Si to lithium carbonate to polypropylene alcohol in the third step is 20:2: 1.
5. The method for preparing the SEI film for the negative electrode of the lithium ion battery as claimed in claim 1, wherein the spray drying mode used in the first step and the third step is open spray drying.
6. The method for preparing the SEI film for the negative electrode of the lithium ion battery as claimed in claim 5, wherein the inlet air temperature during the open spray drying is 150-300 ℃; the air outlet temperature is 60-120 ℃.
7. The lithium ion battery cathode material is characterized in that the cathode material is SiOx @ Si/Li2SiO3a/C composite material.
8. The lithium ion battery negative electrode material of claim 7, wherein the SiOx @ Si/Li obtained by the method for preparing the SEI film of the lithium ion battery negative electrode of claim 1 is2SiO3Ultrasonically mixing the composite material and an organic carbon source through an aqueous solution, placing the powder collected after spray drying into a tubular furnace, and treating for 5-7h at the temperature of 600-800 ℃ in the atmosphere of hydrogen-argon mixed gas to obtain the lithium ion battery cathode material.
9. The lithium ion battery negative electrode material of claim 8, wherein the organic carbon source is one of phenolic resin, glucose, vitamin C and sucrose.
10. Use of a lithium ion battery negative electrode material according to any one of claims 7 to 9 in the preparation of a lithium ion battery.
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| CN112125294A (en) * | 2020-09-21 | 2020-12-25 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| CN112133898A (en) * | 2020-09-21 | 2020-12-25 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based negative electrode material and preparation method thereof |
| CN112142060A (en) * | 2020-09-21 | 2020-12-29 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
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| CN112447956A (en) * | 2020-11-27 | 2021-03-05 | 深圳市德方纳米科技股份有限公司 | Composite silicon-based negative electrode material, preparation method thereof and lithium ion battery |
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| CN112164779A (en) * | 2020-09-24 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Carbon-coated silicon-based negative electrode material and preparation method thereof |
| CN112164779B (en) * | 2020-09-24 | 2022-03-08 | 长沙矿冶研究院有限责任公司 | Carbon-coated silicon-based negative electrode material and preparation method thereof |
| CN112447956A (en) * | 2020-11-27 | 2021-03-05 | 深圳市德方纳米科技股份有限公司 | Composite silicon-based negative electrode material, preparation method thereof and lithium ion battery |
| CN112670453A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based laminated anode material and preparation method and application thereof |
| CN114804116A (en) * | 2021-01-28 | 2022-07-29 | 中国科学院青岛生物能源与过程研究所 | Modified preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN114804116B (en) * | 2021-01-28 | 2024-04-16 | 中国科学院青岛生物能源与过程研究所 | Modification preparation method of silicon oxide negative electrode material of lithium ion battery |
| CN113130868A (en) * | 2021-04-09 | 2021-07-16 | 昆山宝创新能源科技有限公司 | Composite material containing silicon monoxide, negative plate, lithium battery and preparation method thereof |
| CN113782858A (en) * | 2021-08-30 | 2021-12-10 | 上海纳米技术及应用国家工程研究中心有限公司 | By SiOxMethod for increasing and recycling negative electrode capacity of lithium ion battery at @ C |
| CN113948688A (en) * | 2021-09-30 | 2022-01-18 | 浙江锂宸新材料科技有限公司 | Modified pre-lithiated silica composite material and preparation method and application thereof |
| CN113964310A (en) * | 2021-11-10 | 2022-01-21 | 陈骏 | Artificial graphite negative electrode material with SEI layer and preparation method and application thereof |
| CN114566619B (en) * | 2021-12-25 | 2023-11-28 | 河南大森林生物科技有限公司 | Green method for preparing lithium ion battery composite anode material by using siliceous biomass |
| CN114566619A (en) * | 2021-12-25 | 2022-05-31 | 河南大森林生物科技有限公司 | Green method for preparing lithium ion battery composite negative electrode material by adopting silicon-containing biomass |
| CN114709389A (en) * | 2022-03-30 | 2022-07-05 | 浙江锂宸新材料科技有限公司 | Pre-lithiation negative electrode material and preparation method and application thereof |
| CN114843496A (en) * | 2022-05-26 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
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