CN114284479B - Preparation method of novel carbon-silicon anode material - Google Patents
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Abstract
The invention relates to the technical field of negative electrode materials, and provides a preparation method of a novel carbon-silicon negative electrode material, which comprises the following steps: s1, mixing and stirring a silane coupling agent, lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution; s2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution; s3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor; and S4, sintering the precursor in an inert atmosphere or a reducing atmosphere to form the carbon-silicon anode material. Through the technical scheme, the problems of low charge and discharge efficiency and poor cycle performance in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a preparation method of a novel carbon-silicon negative electrode material.
Background
With the continuous increase of the requirements of new energy automobiles on the endurance mileage in practical application, the related materials of the power battery are also developed towards the direction of providing higher energy density. The graphite cathode of the traditional lithium ion battery can not meet the existing requirements, and the high-energy-density cathode material becomes a new hot spot for research pursuit.
The silicon-based material cathode is gradually the most preferred choice for improving the cathode of battery enterprises and lithium battery materials due to rich reserves and ultrahigh theoretical specific capacity (3840 mAh/g), and is one of the cathode materials of the next generation lithium ion battery with the highest potential. However, silicon materials have obvious disadvantages as battery cathode materials: firstly, the volume expansion of silicon is 100% -300% in the charge and discharge process, the SEI film is continuously destroyed by a huge volume effect, the capacity of a lithium ion battery is continuously reduced, the cycle attenuation is serious, and the service life is reduced; second, silicon is a semiconductor, conductivity is much worse than that of graphite, so that irreversible degree is large in the lithium ion deintercalation process, initial coulombic efficiency is further reduced, a Li 22Si5 alloy phase is formed after the silicon-based material is intercalated with lithium, serious volume expansion (up to 300%) exists in the deintercalation/intercalation process, cracking and even pulverization of active substances are easily caused, electrical contact between the active substances and a current collector is damaged, and cycle life is greatly shortened. Silicon oxide shows a small volume change during the cycle as compared with elemental silicon, and byproducts such as lithium oxide and lithium silicate generated in situ during the first lithiation process can buffer the volume change and improve the stability of the cycle. However, siO x -based anode materials irreversibly consume Li + to form Li 2 O and lithium silicate in the first cycle, resulting in a relatively low initial coulombic efficiency (first coulombic efficiency) of the silicon oxide.
The carbonaceous anode material has smaller volume change in the charge and discharge process and better cycle stability, and the carbonaceous anode material is a mixed conductor of ions and electrons; in addition, silicon has similar chemical properties to carbon, and the two can be closely combined, so carbon is often used as a preferred matrix for compounding with silicon. In the Si/C composite system, si particles are used as active substances to provide lithium storage capacity; and C, not only can buffer the volume change of the silicon cathode in the charge and discharge process, but also can improve the conductivity of the Si material, and can avoid agglomeration of Si particles in the charge and discharge cycle. Therefore, the Si/C composite material combines the advantages of the Si/C composite material and has high specific capacity and long cycle life, and is expected to replace graphite to become a new generation of lithium ion battery anode material. The existing silicon-carbon negative electrode coating method generally adds silicon powder and solid carbon source into a mixer for mixing, and the mixture containing the coating layer is roasted under inert atmosphere to obtain a silicon-based composite material coated with carbon, and then the silicon-carbon composite material is mixed with graphite material to obtain the silicon-carbon negative electrode material.
Disclosure of Invention
The invention provides a preparation method of a novel carbon-silicon anode material, which solves the problems in the related art.
The technical scheme of the invention is as follows:
the preparation method of the novel carbon-silicon anode material comprises the following steps:
S1, mixing and stirring a silane coupling agent, lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution;
S2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution;
S3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor;
And S4, sintering the precursor in an inert atmosphere or a reducing atmosphere to form the carbon-silicon anode material.
As a further technical scheme, the silane coupling agent is one or more of aminosilane, epoxy silane, thio silane, methacryloxy silane, vinyl silane, ureido silane, isocyanato silane, tetraethoxysilane and vinyl triethoxy silane.
As a further technical scheme, the lithium salt is lithium acetate and/or lithium hydroxide, and the organic carbon source is one or more of polyethylene glycol, phenolic resin and epoxy resin.
As a further technical scheme, the surfactant is one or more of cetyl ammonium bromide, stearyl trimethyl ammonium bromide and stearyl trimethyl ammonium bromide.
As a further technical scheme, the solvent in the step S1 is one or more of water, dimethylformamide, isopropanol, glacial acetic acid and absolute ethyl alcohol. As a further technical scheme, in the step S1, the mass-volume ratio of the silane coupling agent, the lithium salt, the carbon, the surfactant, the polyacrylonitrile and the solvent is (5-20 ml): (0.l-1 g): (0.l-1 g): (0.l-1 g): (0.l-1 g): (100 ml-500 ml).
As a further technical scheme, the solvent used in the metal salt solution in the step S2 is one of water, isopropanol and alcohol.
As a further technical scheme, in the step S2, the metal salt is one of aluminum isopropoxide, butyl titanate and zinc acetate.
As a further technical scheme, in the step S2, the mass-volume ratio of the metal salt to the solvent to the polyvinylpyrrolidone is (5-20 ml) (100-500 ml) (0.5-2 g).
As a further technical scheme, in the step S4, the sintering temperature is 600-900 ℃ and the sintering time is 60-180 min.
As a further technical scheme, in the step S3, spinning is performed under the condition of an external electric field of 10-50 kv.
The beneficial effects of the invention are as follows:
1. Based on the characteristic that the nanofiber has the characteristic of rapidly transmitting electrons and ions, the invention designs and synthesizes the SiO x/C@MOy (M=Ti, si, al) coaxial nanofiber lithium ion battery anode material with a novel structure. The SiO x nanofiber obviously improves the diffusion rate of Li + by reducing the ion diffusion path; the carbon nanofiber can remarkably improve the electronic conductivity of the material and provide a buffer space for the volume expansion of the battery in the charge and discharge process; the excellent mechanical property of the metal oxide shell can inhibit the active material from falling off or powdering due to Li + insertion/extraction, so that the cycle performance of the active material is improved; the addition of lithium salt can improve the first charge-discharge efficiency of the active material. The transition metal doping can promote the decomposition of irreversible Li 2 O, so that the first charge and discharge efficiency of the active material is improved. The combined action of the advantages can lead the SiO x/C@MOy (M=Ti, si, al) coaxial nanofiber lithium ion battery anode material to have the characteristics of good electrochemical performance, stable structure and the like.
2. According to the invention, the SiO x/C with the core-shell structure and the metal oxide coating layer can effectively buffer the volume expansion of the active substance in the charge-discharge process, and meanwhile, the carbon shell layer with excellent mechanical property can inhibit the falling of the active substance, so that the cycle performance of the material is greatly improved.
3. The nanofiber material Li + has the advantages of short diffusion path, large specific surface area and large porosity, can effectively promote the rapid insertion/extraction of Li +, provide sufficient transport channels for electrolyte ions, lead more electrolyte ions to participate in electrochemical reaction, and is beneficial to effectively exerting the electrochemical performance of active substances.
4. The addition of the lithium salt can promote the decomposition of irreversible Li 2 O by the transition metal doping, so that the first charge and discharge efficiency of the active material is improved, and the falling-off of the active material caused by volume expansion is relieved.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
Fig. 1 is a specific charge capacity of example 2 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) 10Ml of vinyltriethoxysilane, 0.2g of lithium acetate, 0.2g of polyethylene glycol, 0.3g of cetylammonium bromide and 0.5g of polyacrylonitrile are dissolved in 150ml of isopropanol and stirred to form an inner shaft spinning solution.
(2) 10Ml of butyl titanate was dissolved in 200ml of alcohol, and 0.5g of polyvinylpyrrolidone polymer matrix was added thereto and stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions are as follows: the spinning distance is 15cm, and the flow rate of the core liquid is 0.25mm/min; the sheath fluid flow rate was 0.25mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 900 ℃ for 60min to form the carbon-silicon anode material.
Example 2
(1) 5Ml of aminosilane, 0.5g of lithium hydroxide, 0.4g of epoxy resin and 0.2g of stearyl trimethylammonium bromide, 1.0g of polyacrylonitrile were dissolved in 200ml of isopropanol and stirred to form an inner shaft dope.
(2) 20Ml of aluminum isopropoxide was dissolved in 500ml of alcohol, 2.0g of polyvinylpyrrolidone polymer matrix was added, and the resultant was stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions are as follows: the spinning distance is 10cm, and the flow rate of the core liquid is 0.20mm/min; the sheath fluid flow rate was 0.20mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 600 ℃ for 180min to form the carbon-silicon anode material.
Example 3
(1) 15Ml of ethyl orthosilicate, 0.8g of lithium acetate, 0.2g of phenolic resin, 0.6g of octadecyl trimethyl ammonium bromide, 0.3g of polyacrylonitrile are dissolved in 300ml of alcohol, and the mixture is stirred to form an inner shaft spinning solution.
(2) 5Ml of zinc acetate was dissolved in 250ml of alcohol, 1.5g of polyvinylpyrrolidone polymer matrix was added, and the resultant was stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 10 kv; the spinning conditions are as follows: the spinning distance is 20cm, and the flow rate of the core liquid is 0.10mm/min; the sheath fluid flow rate was 0.10mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 800 ℃ for 120min to form the carbon-silicon anode material.
Example 4
(1) 8.0Ml of isocyanatosilane, 0.2g of lithium acetate, 0.5g of epoxy resin, 0.3g of cetylammonium bromide, 0.1g of polyacrylonitrile are dissolved in 100ml of isopropanol and stirred to form an inner shaft spinning solution.
(2) 5Ml of aluminum isopropoxide was dissolved in 100ml of alcohol, 0.5g of polyvinylpyrrolidone polymer matrix was added, and the resultant was stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 50 kv; the spinning conditions are as follows: the spinning distance is 10cm, and the flow rate of the core liquid is 0.20mm/min; the sheath fluid flow rate was 0.20mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 700 ℃ for 60min to form the carbon-silicon anode material.
Example 5
(1) 5Ml of vinylsilane, 0.1g of lithium acetate, 0.1g of polyethylene glycol, 1.0g of cetylammonium bromide and 1.0g of polyacrylonitrile were dissolved in 300ml of water, and stirred to form an inner shaft spinning solution.
(2) 20Ml of zinc acetate was dissolved in 500ml of alcohol, 2.0g of polyvinylpyrrolidone polymer matrix was added, and the resultant was stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 30 kv; the spinning conditions are as follows: the spinning distance is 10cm, and the flow rate of the core liquid is 0.15mm/min; the sheath fluid flow rate was 0.15mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 900 ℃ for 120min to form the carbon-silicon anode material.
Control group
(1) 10Ml of vinyltriethoxysilane was dissolved in 150ml of isopropanol and stirred to form an inner shaft dope.
(2) 0.5G of polyvinylpyrrolidone polymer matrix was dissolved in 200ml of alcohol and stirred to form an outer shaft dope.
(3) Spinning the solution under the condition of an external electric field of 15 kv; the spinning conditions are as follows: the spinning distance is 15cm, and the flow rate of the core liquid is 0.25mm/min; the sheath fluid flow rate was 0.25mm/min.
(4) And (3) transferring the obtained precursor into an argon atmosphere, and performing heat treatment at 900 ℃ for 60min to form the carbon-silicon anode material.
Experimental example
The silicon-carbon negative electrode materials obtained in examples 1 to 5 and the control group were assembled into a lithium ion battery, a metal lithium sheet was used as a counter electrode, a polypropylene porous membrane Celgard2400 was used as a separator, a mixed solution of 1mol/L of LiPF 6 in Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) (the volume ratio of EMC: DMC was 1:1:1) was used as an electrolyte, a coin cell (CR 2032) was assembled in an argon glove box, and after standing for 24 hours, a charge and discharge test was performed on a New Wick CT-4008 tester. The results are shown in Table 1.
Table 1 comparison of the Properties of examples 1 to 5 with the control group
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the carbon-silicon anode material is characterized by comprising the following steps of:
S1, mixing and stirring a silane coupling agent, lithium salt, a carbon source, a surfactant, polyacrylonitrile and a solvent to prepare an inner shaft spinning solution;
S2, stirring the metal salt solution and polyvinylpyrrolidone to prepare an outer shaft spinning solution;
S3, spinning the inner shaft spinning solution and the outer shaft spinning solution to prepare a precursor;
s4, sintering the precursor in an inert atmosphere to obtain a metal oxide shell, and forming the carbon-silicon anode material;
the lithium salt is lithium acetate and/or lithium hydroxide;
in the step S2, the metal salt is one of aluminum isopropoxide, butyl titanate and zinc acetate;
the carbon source is one or more of polyethylene glycol, phenolic resin and epoxy resin.
2. The method for preparing the carbon-silicon anode material according to claim 1, wherein the silane coupling agent is one or more of aminosilane, epoxysilane, thiosilane, methacryloxy silane, vinyl silane, ureido silane, isocyanato silane and tetraethyl orthosilicate.
3. The method for preparing the carbon-silicon anode material according to claim 1, wherein the surfactant is one or more of cetylammonium bromide, octadecyltrimethylammonium bromide and stearyl trimethylammonium bromide.
4. The method for preparing a carbon-silicon negative electrode material according to claim 1, wherein the solvent in the step S1 is one or more of water, dimethylformamide, isopropanol, glacial acetic acid, and absolute ethanol.
5. The preparation method of the carbon-silicon anode material according to claim 1, wherein in the step S1, the mass-volume ratio of the silane coupling agent, the lithium salt, the carbon source, the surfactant, the polyacrylonitrile and the solvent is (5-20 ml): (0.1-1 g): (0.1-1 g): (0.1-1 g): (0.1-1 g): (100 ml to 500 ml).
6. The method for preparing a carbon-silicon negative electrode material according to claim 1, wherein the solvent used in the metal salt solution in the step S2 is one of water, isopropanol and alcohol.
7. The preparation method of the carbon-silicon anode material according to claim 6, wherein in the step S2, the mass-volume ratio of the metal salt to the solvent to the polyvinylpyrrolidone is (5-20 ml): (100-500 ml): (0.5-2 g).
8. The method for preparing a carbon-silicon negative electrode material according to claim 1, wherein in the step S4, the sintering temperature is 600-900 ℃ and the sintering time is 60-180 min.
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