Cellulose in-situ carbon-based lithium battery aerogel and preparation method thereof
Technical Field
The invention relates to the technical field of solid-state lithium batteries, in particular to cellulose in-situ carbon-based lithium battery aerogel and a preparation method thereof.
Background
Through decades of development, lithium batteries have become the most widely used energy storage units in daily life, and are mainly used in digital products such as mobile phone batteries and notebook batteries, as well as in battery automobiles and the like. With the gradual weight reduction, miniaturization and high integration of electronic products, the requirements for batteries are also increasing. The specific energy, shape and safety of the battery greatly limit the development of the current electronic products such as mobile phones, notebook computers and unmanned aerial vehicles, so that the most urgent problem is to find a novel high specific energy electrode material to improve the energy storage performance of the battery, so that the development progress of the related industries can be followed.
The novel lithium battery cathode material mainly comprises a graphene material, a silicon-carbon material and a tin-carbon material, the graphene material is difficult to realize industrial production of the battery material due to high production cost, the silicon-carbon material also limits the commercialization progress due to large volume expansion in the charging and discharging process, and compared with the former two materials, the tin-carbon material is low in price, belongs to one of five metals of gold, silver, copper, iron and tin, is mature in production technology and has a good commercialization prospect.
Elemental tin has good lithium storage performance, but also has the problem of volume expansion, so that a carbon material is required to be adopted for processing processes such as doping modification or coating. The existing doping is mainly ball milling compounding, a carbon source and a tin material are fully mixed in a ball milling environment to prepare a particle material with a micro-nano particle size, and the performance of the tin-carbon material is improved. However, the ball milling time is too long, the energy consumption is too high, the large-scale industrial production is difficult, and the application of the ball milling is limited. The other method is a template method, a micro composite structure is formed by other substances and a carbon source, the other substances are dissolved by using special solvents to leave a porous carbon source micro structure, and then a tin source is filled in to form a carbon-coated tin structure, so that the high-capacity cathode material is realized. Compared with the former method, the method has better performance, but the preparation process is more complicated, the consistency of the product is difficult to guarantee, and the method has some uncertain factors on the performance of the battery.
The performance of the negative electrode material of the battery plays a crucial role in the overall performance of the battery, and is an indispensable role in four major components of lithium batteries. In the prior art, the large-scale industrial production is difficult to realize mainly due to the limitation of the production process and the production cost, and in order to make up for the blank of the prior art, the invention provides a method for preparing a cellulose in-situ carbon-based lithium battery tin-carbon aerogel negative electrode material machine.
Disclosure of Invention
Aiming at the problems of the conventional lithium battery cathode material, the invention aims to provide cellulose in-situ carbon-based lithium battery aerogel and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of cellulose in-situ carbon-based lithium battery aerogel comprises the following steps:
(1) dispersing at least one of nano tin, stannic chloride and stannous chloride as a tin source in 60-100 parts by weight of water to form a homogeneously dispersed tin solution system; the total amount of tin contained in the tin source is 2-8 parts by weight;
(2) adding 4-10 parts by weight of hydroxyethyl cellulose into a tin solution system, and stirring at normal temperature to fully dissolve the hydroxyethyl cellulose to form transparent or semitransparent sticky liquid;
(3) adding an alkali solution into the viscous liquid, continuously stirring uniformly, adding 5-150 parts by weight of a cross-linking agent, stirring uniformly at normal temperature, and finally polymerizing at normal temperature to form transparent or semitransparent blocky gel;
(4) and drying the obtained gel, and then carbonizing, ball-milling and washing the dried gel to obtain the cellulose in-situ carbon-based lithium battery aerogel.
In a preferable mode, the preparation method comprises the step of preparing nano tin by a reduction method, wherein the nano tin is prepared from one or more of tin chloride, stannous chloride or tin powder, the adopted reducing agent is sodium borohydride or potassium borohydride, the total amount of tin in the raw materials is 2-8 parts by weight, and the amount of the sodium borohydride or the potassium borohydride is 2-15 parts by weight.
Preferably, in the preparation method, the alkali solution in the step (3) is 10 to 50 parts by weight of sodium hydroxide or 15 to 60 parts by weight of potassium hydroxide and water in a ratio of 1 g: 4ml of the mixture.
Preferably, in the preparation method, the crosslinking agent in the step (3) is selected from one or more of epichlorohydrin, succinic anhydride, succinyl chloride, divinyl sulfone, polybasic acid and N, N-methylene bisacrylamide.
Preferably, in the preparation method, the molecular weight of the hydroxyethyl cellulose is 9-72 ten thousand. This ensures that the polymer crosslinks to form a gel.
Preferably, in the preparation method, the mixing and stirring time of the hydroxyethyl cellulose and the tin solution system in the step (2) is 0.5 to 2 hours. This enables uniform mixing.
Preferably, in the preparation method, the gel crosslinking temperature in the step (3) is controlled to be 20-50 ℃, and the crosslinking time is 3-10 hours, so that the crosslinking can be fully performed in such time.
Preferably, in the preparation method, the drying method of the gel in the step (4) is one of supercritical drying, freeze drying, vacuum drying and forced air drying, the drying time of the gel is 0.5-4 days, and the drying temperature is-50-70 ℃ so as to be sufficiently dried.
Preferably, in the preparation method, the gel carbonization temperature in the step (4) is 800-1600 ℃, and the heat preservation time is 1-4 hours, so that the carbonization can be fully performed.
In order to realize the aim, the invention also provides the cellulose in-situ carbon-based lithium battery aerogel prepared by the preparation method.
Compared with the prior tin-carbon lithium battery cathode technology, the preparation method of the cellulose in-situ carbon-based lithium battery aerogel has the outstanding characteristics and excellent effects that:
1. according to the invention, the hydroxyethyl cellulose raw material which is the most abundant biomass raw material in the nature is used, the prepared cellulose in-situ carbon-based lithium battery aerogel has excellent performance, has good gram capacity in the lithium battery cathode material, and simultaneously ensures that the cellulose in-situ carbon-based lithium battery aerogel has good preparation process and excellent specific surface area, so that the cellulose in-situ carbon-based lithium battery aerogel has important promotion significance for application development of the lithium battery cathode material, and a short plate of the conventional lithium battery cathode material is supplemented.
2. The preparation method has the advantages of wide sources of the raw materials, simple preparation method and low preparation cost, the adopted raw materials are all from industrialized products, the preparation feasibility is strong, the industrialization difficulty is small, and the industrial large-scale production is expected to be realized.
Drawings
FIG. 1 is a schematic diagram of the chemical crosslinking process for preparing a crosslinked gel according to the present invention.
FIG. 2 is an SEM image of a chemically crosslinked gel prepared according to the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
FIG. 2 is an SEM image of a chemically crosslinked gel prepared according to the present invention. It can be seen from FIG. 2 that the crosslinked gel has a continuous uniform structure.
Example 1
A preparation method of cellulose in-situ carbon-based lithium battery aerogel comprises the following steps:
(1) the nano tin is prepared by a reduction method, the raw material of the nano tin is one or more of tin chloride, stannous chloride or tin powder, the adopted reducing agent is sodium borohydride, the total amount of tin in the raw material is 2-8 parts by weight, and the sodium borohydride is 2 parts by weight.
Dispersing nano tin as a tin source in 60 parts by weight of water to form a homogeneously dispersed tin solution system; the total amount of tin contained in the tin source is 2-8 parts by weight;
(2) adding 4 parts by weight of hydroxyethyl cellulose into a tin solution system, and stirring for 0.5 hour at normal temperature to fully dissolve the hydroxyethyl cellulose to form transparent or semitransparent sticky liquid; the molecular weight of the hydroxyethyl cellulose is 9-72 ten thousand.
(3) Adding an alkali solution into the viscous liquid, continuously stirring uniformly, adding 5 parts by weight of cross-linking agent epichlorohydrin, stirring uniformly at normal temperature, and finally polymerizing at normal temperature to form transparent or semitransparent blocky gel; the alkali solution is 10 parts by weight of sodium hydroxide and water according to the weight ratio of 1 g: 4ml of the mixture. The gel crosslinking temperature was controlled at 20 ℃ and the crosslinking time was 3 hours.
(4) Drying the obtained gel in supercritical manner for 0.5 days at-50 deg.C. And carbonizing the dried gel at 800 ℃ for 1 hour, and then performing ball milling and washing treatment to obtain the cellulose in-situ carbon-based lithium battery aerogel.
Example 2
A preparation method of cellulose in-situ carbon-based lithium battery aerogel comprises the following steps:
(1) dispersing tin tetrachloride serving as a tin source in 100 parts by weight of water to form a homogeneously dispersed tin solution system; the total amount of tin contained in the tin source is 2-8 parts by weight;
(2) adding 10 parts by weight of hydroxyethyl cellulose into a tin solution system, wherein the molecular weight of the hydroxyethyl cellulose is 9-72 ten thousand, and stirring for 2 hours at normal temperature to fully dissolve the hydroxyethyl cellulose to form transparent or semitransparent sticky liquid;
(3) adding an alkali solution into the viscous liquid, and continuously stirring uniformly, wherein the alkali solution is 15 parts by weight of potassium hydroxide and water according to the weight ratio of 1 g: 4ml of the mixture is prepared, then 150 parts by weight of cross-linking agent succinic anhydride is added and evenly stirred at normal temperature, the gel cross-linking temperature is controlled at 50 ℃, and the cross-linking time is 10 hours. Finally, polymerizing at normal temperature to form transparent or semitransparent blocky gel;
(4) drying the obtained gel in vacuum for 4 days at 70 deg.C. And carbonizing the dried gel, wherein the gel carbonization temperature is 1600 ℃, the heat preservation time is 4 hours, and then performing ball milling and washing treatment to obtain the cellulose in-situ carbon-based lithium battery aerogel.
Example 3
A preparation method of cellulose in-situ carbon-based lithium battery aerogel comprises the following steps:
(1) dispersing stannous chloride serving as a tin source in 70 parts by weight of water to form a homogeneously dispersed tin solution system; the total amount of tin contained in the tin source is 2-8 parts by weight;
(2) 6 parts by weight of hydroxyethyl cellulose having a molecular weight of 9 to 72 ten thousand is added to the tin solution system. Stirring at normal temperature to fully dissolve the mixture to form transparent or semitransparent sticky liquid;
(3) adding an alkali solution into the viscous liquid, and continuously stirring for 1 hour, wherein the alkali solution is 30 parts by weight of sodium hydroxide and water according to the weight ratio of 1 g: 4ml of the mixture. Adding 50 parts by weight of cross-linking agent divinyl sulfone, uniformly stirring at normal temperature, controlling the gel cross-linking temperature to be 30 ℃, controlling the cross-linking time to be 5 hours, and finally polymerizing at normal temperature to form transparent or semitransparent blocky gel;
(4) drying the obtained gel in a freeze drying mode, wherein the drying time of the gel is 1 day, the drying temperature is-20 ℃, carbonizing the dried gel, the carbonizing temperature of the gel is 1200 ℃, the heat preservation time is 2 hours, and then performing ball milling and washing treatment to obtain the cellulose in-situ carbon-based lithium battery aerogel.
Example 4
A preparation method of cellulose in-situ carbon-based lithium battery aerogel comprises the following steps:
(1) the nano tin is prepared by a reduction method, the raw materials of the nano tin are tin chloride and tin powder, the adopted reducing agent is potassium borohydride, and the weight part of the potassium borohydride is 15.
Dispersing nano tin and stannic chloride serving as tin sources in 80 parts by weight of water to form a homogeneously dispersed tin solution system; the total amount of tin contained in the tin source is 2-8 parts by weight;
(2) to the tin solution system was added 8 parts by weight of hydroxyethyl cellulose having a molecular weight of 9-72 ten thousand. Stirring for 1.5 hours at normal temperature to fully dissolve the mixture to form transparent or semitransparent sticky liquid;
(3) adding an alkali solution into the viscous liquid, and continuously stirring uniformly, wherein the alkali solution is prepared from 35 parts by weight of potassium hydroxide and water according to the weight ratio of 1 g: 4ml of the mixture. And adding 120 parts by weight of cross-linking agent, uniformly stirring at normal temperature, wherein the cross-linking agent comprises divinyl sulfone, polybasic acid and N, N-methylene bisacrylamide, the gel cross-linking temperature is controlled at 40 ℃, and the cross-linking time is 6 hours, so that the gel can be fully cross-linked in such time. Finally, polymerizing at normal temperature to form transparent or semitransparent blocky gel;
(4) and drying the obtained gel by blowing air for 3 days at the drying temperature of 40 ℃, carbonizing the dried gel at the gel carbonization temperature of 1400 ℃ for 3 hours, and fully carbonizing. And then ball-milling and washing to obtain the cellulose in-situ carbon-based lithium battery aerogel.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.