CN108417410B - Cellulose gel electrolyte material and preparation method thereof - Google Patents

Cellulose gel electrolyte material and preparation method thereof Download PDF

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CN108417410B
CN108417410B CN201810049383.XA CN201810049383A CN108417410B CN 108417410 B CN108417410 B CN 108417410B CN 201810049383 A CN201810049383 A CN 201810049383A CN 108417410 B CN108417410 B CN 108417410B
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sodium hydroxide
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王丽秋
张晓博
刘学龙
刘洋
郭晨晓
侯亚娟
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Yanshan University
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    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • C08J2301/02—Cellulose; Modified cellulose
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

A cellulose gel electrolyte material is prepared by taking natural cellulose wood pulp, paper pulp, bamboo pulp or absorbent cotton as raw materials, reacting with sodium hydroxide and carbon disulfide to synthesize cellulose viscose, and forming gel cellulose gel electrolyte material through hydration treatment; the preparation method mainly comprises the steps of reacting paper pulp (wood pulp, bamboo pulp or absorbent cotton) with sodium hydroxide and carbon disulfide for 30-60min to prepare orange viscose, mixing the viscose with deionized water according to the weight ratio of 1:1-9, gelling to obtain the cellulose gel electrolyte material, and adding potassium ferrocyanide or acetonitrile solution of potassium iodide and iodine to prepare the composite cellulose gel electrolyte material. The method is simple, the product is easy to form, the operation and the control are simple and convenient, and the method is beneficial to industrial production; the prepared cellulose gel electrolyte material is a porous gel polymer, has good liquid retention capacity and ionic conductivity, and can be applied to super capacitors, solar cells, lithium batteries and the like.

Description

Cellulose gel electrolyte material and preparation method thereof
Technical Field
The invention relates to an electrolyte material and a preparation method thereof.
Background
Electrolytes are classified into three categories according to their presence: the electrolyte comprises a liquid electrolyte, a solid electrolyte and a gel electrolyte, wherein the liquid electrolyte has the highest conductivity, but has the problems of easy leakage, difficult packaging, easy volatilization of used solvents, poor long-term stability and the like. Solid electrolytes can overcome such problems, but their conductivity is low and commercialization is currently difficult. The gel electrolyte has the advantages of both liquid electrolyte and solid electrolyte, is an ideal electrolyte material, is mainly a polymer hydrogel based on polyvinyl alcohol (PVA) and polyethylene glycol (PEG), has few varieties and single raw material for preparing a matrix, cannot meet the requirements of the current science and technology and market development, and still needs to be usedFurther development is carried out. Especially when such hydrogels are currently used in flexible supercapacitors, PVA or PEG and H are used2SO4(or other acids, bases, salts) in this case, the state is not a true gel film, and although a physical gel film can be formed by evaporation of a large amount of water, in this case, a high water content and a high mechanical strength cannot be simultaneously achieved, and it is difficult to achieve a state of a self-supporting film.
Disclosure of Invention
The invention aims to provide a chemically crosslinked self-supporting cellulose gel electrolyte material which has simple preparation method, easy product forming, simple and convenient operation and control and environmental protection, and a preparation method thereof.
The cellulose gel electrolyte material is prepared by using wood pulp, paper pulp, bamboo pulp or absorbent cotton which is made of natural cellulose as raw materials, reacting the raw materials with sodium hydroxide and carbon disulfide to synthesize cellulose viscose, and forming gel through hydration treatment.
The preparation method of the cellulose gel electrolyte material comprises the following steps:
(1) adding natural cellulose into 16-40% by mass of sodium hydroxide solution according to the proportion of adding 3-6mL of sodium hydroxide solution into per gram of natural cellulose, after uniform dispersion, firstly preserving heat for 10-30min at 25-30 ℃, then adding 1-2.5mL of carbon disulfide into per gram of natural cellulose, reacting for 30-60min, after conversion to an orange solid state, adding 4% by mass of sodium hydroxide solution according to the proportion of adding 6-12mL of sodium hydroxide solution into per gram of natural cellulose, and stirring until the mixture is completely uniform orange viscose.
The natural cellulose is paper pulp, wood pulp, bamboo pulp or absorbent cotton.
(2) And (2) mixing the viscose liquid prepared in the step (1) with deionized water according to the weight ratio of 1:1-9, uniformly stirring, standing and crosslinking for 48-72 hours to obtain the cellulose gel electrolyte (XWD).
Or mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.1-0.41-9, evenly stirring, standing and crosslinking for 48-72 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
Or washing the prepared cellulose gel electrolyte (XWD) with deionized water to neutrality, soaking in acetonitrile solution of potassium iodide and iodine, wherein the concentration of potassium iodide is 0.02-0.1mol/L, the concentration of iodine is 0.01-0.05mol/L, and KI/I is obtained after 12-24 hr2Cellulose gel electrolyte (XWD-KI/I)2)。
Compared with the prior art, the invention has the following advantages:
1. the natural cellulose pulp, wood pulp, bamboo pulp or absorbent cotton are used as raw materials, and the raw materials are convenient to obtain, low in price and environment-friendly.
2. The prepared cellulose gel electrolyte is derived from natural cellulose, so that the product is safe to use, green and environment-friendly, has good biocompatibility and is beneficial to wide application.
3. The preparation method is simple, the product is easy to form, the operation and control are simple and convenient, the environment is friendly, and the method is beneficial to industrial production.
4. The prepared cellulose gel electrolyte is in an crosslinked network structure, is a porous gel polymer, has good liquid retention capacity, ionic conductivity and mechanical property, can be used as a quasi-solid electrolyte, improves the problems that a liquid electrolyte is difficult to package, easy to leak, unstable and the like, and is widely applied to super capacitors, solar cells, metal ion batteries and the like.
5. Can improve the property of electrolyte or be made into other kinds of gel materials.
6. The prepared cellulose gel electrolyte material is washed by water to different pH values, and is compounded with other electrolytes or substances (such as potassium ferrocyanide or acetonitrile solution of potassium iodide and iodine) to prepare other electrolytes or gel materials.
7. Can form a self-supporting gel electrolyte film and is very important for flexible supercapacitors.
Drawings
FIG. 1 is a schematic representation of a cellulose gel electrolyte prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a cellulose gel electrolyte prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of an electrolyte of a cellulose gel produced in example 1 of the present invention.
FIG. 4 is a cyclic voltammogram of a supercapacitor assembled from the cellulose gel electrolyte prepared in example 1 of the present invention and the potassium ferrocyanide-cellulose gel electrolyte prepared in example 5.
FIG. 5 is a constant current charge and discharge diagram of a supercapacitor assembled from the cellulose gel electrolyte prepared in example 1 of the present invention and the potassium ferrocyanide-cellulose gel electrolyte prepared in example 5.
FIG. 6 is a graph of IPCE of potassium iodide, iodine-cellulose gel electrolyte prepared in example 9 of the present invention.
The specific implementation mode is as follows:
example 1
(1) Adding 1g of natural cellulose into 3mL of 16% sodium hydroxide solution, uniformly dispersing, then preserving heat for 10min at 25 ℃, then adding 1mL of carbon disulfide, reacting for 30min, adding 6mL of 4% sodium hydroxide solution after the product is converted into an orange solid, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1:1, uniformly stirring, standing and crosslinking for 48 hours to obtain the cellulose gel electrolyte (XWD).
As shown in FIG. 1, the prepared cellulose gel electrolyte contains a large amount of water and has certain toughness.
As shown in fig. 2, after drying and grinding the gel electrolyte, the gel electrolyte was coated on a conductive tape and tested by a scanning electron microscope, it was found that the inner pore diameter was about 1 μm, and the actual pore diameter was more than 1 μm because the gel electrolyte shrunk when dried.
As shown in fig. 3, it can be seen that the gel electrolyte has a relatively good crystallinity, with relatively strong characteristic diffraction peaks at 32.4 °, 37.9 °, and relatively weak characteristic diffraction peaks at 40.2 °, 41.3 °, and 45.0 °.
As shown in fig. 5, it can be seen that the XWD system assembled into a supercapacitor has charge and discharge capability.
Example 2
(1) Adding 1g of natural cellulose into 4mL of sodium hydroxide solution with the mass fraction of 18%, uniformly dispersing, then preserving heat for 20min at 26 ℃, then adding 1.5mL of carbon disulfide, reacting for 40min, adding 8mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 3, mixing, uniformly stirring, standing and crosslinking for 50 hours to obtain the cellulose gel electrolyte (XWD).
Example 3
(1) Adding 1g of natural cellulose into 5mL of sodium hydroxide solution with the mass fraction of 30%, uniformly dispersing, then preserving heat for 20min at 28 ℃, then adding 2mL of carbon disulfide, reacting for 50min, adding 10mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 6, mixing, uniformly stirring, standing and crosslinking for 60 hours to obtain the cellulose gel electrolyte (XWD).
Example 4
(1) Adding 1g of natural cellulose into 6mL of sodium hydroxide solution with the mass fraction of 40%, uniformly dispersing, firstly preserving the temperature for 30min at the temperature of 30 ℃, then adding 2.5mL of carbon disulfide, reacting for 60min, adding 12mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 9, mixing, stirring uniformly, standing and crosslinking for 72 hours to obtain the cellulose gel electrolyte (XWD).
Example 5
(1) Adding 1g of natural cellulose into 3mL of 16% sodium hydroxide solution, uniformly dispersing, then preserving heat for 10min at 25 ℃, then adding 1mL of carbon disulfide, reacting for 30min, adding 6mL of 4% sodium hydroxide solution after the product is converted into an orange solid, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.1:1, uniformly stirring, standing and crosslinking for 48 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
As shown in FIG. 5, it can be seen that XWD-K4[Fe(CN)6]The super capacitor assembled by the system has charge and discharge capacity, and K is added4[Fe(CN)6]The gel electrolyte of (2) obviously improves the capacitance of the super capacitor due to the existence of Faraday pseudocapacitance.
Example 6
(1) Adding 1g of natural cellulose into 4mL of sodium hydroxide solution with the mass fraction of 18%, uniformly dispersing, then preserving heat for 20min at 26 ℃, then adding 1.5mL of carbon disulfide, reacting for 40min, adding 8mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.2:3, uniformly stirring, standing and crosslinking for 50 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
Example 7
(1) Adding 1g of natural cellulose into 5mL of sodium hydroxide solution with the mass fraction of 30%, uniformly dispersing, then preserving heat for 20min at 28 ℃, then adding 2mL of carbon disulfide, reacting for 50min, after the product is converted into an orange solid state, adding 10mL of sodium hydroxide with the mass fraction of 4% for dissolving, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.3:6, uniformly stirring, standing and crosslinking for 60 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
Example 8
(1) Adding 1g of natural cellulose into 6mL of sodium hydroxide solution with the mass fraction of 40%, uniformly dispersing, firstly preserving the temperature for 30min at the temperature of 30 ℃, then adding 2.5mL of carbon disulfide, reacting for 60min, adding 12mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.4:9, uniformly stirring, standing and crosslinking for 72 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
Example 9
(1) Adding 1g of natural cellulose into 3mL of 16% sodium hydroxide solution, uniformly dispersing, then preserving heat for 10min at 25 ℃, then adding 1mL of carbon disulfide, reacting for 30min, adding 6mL of 4% sodium hydroxide solution after the product is converted into an orange solid, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1:1, uniformly stirring, standing and crosslinking for 48 hours to obtain the cellulose gel electrolyte (XWD).
(3) Washing the cellulose gel electrolyte (XWD) prepared in the step (2) with deionized water to be neutral, then soaking the cellulose gel electrolyte (XWD) in an acetonitrile solution of potassium iodide and iodine, wherein the concentration of the potassium iodide is 0.02mol/L, the concentration of the iodine is 0.01mol/L, and obtaining KI/I after 12 hours2Cellulose gel electrolyte (XWD-KI/I)2)。
As shown in FIG. 6, it can be seen that XWD-KI/I2Has relatively good photoelectric conversion efficiency in the wavelength range of 300nm-1000nmThe dye-sensitized solar cell can be used for dye-sensitized solar cells.
Example 10
(1) Adding 1g of natural cellulose into 4mL of sodium hydroxide solution with the mass fraction of 18%, uniformly dispersing, then preserving heat for 20min at 26 ℃, then adding 1.5mL of carbon disulfide, reacting for 40min, adding 8mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 10min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 3, mixing, uniformly stirring, standing and crosslinking for 50 hours to obtain the cellulose gel electrolyte (XWD).
(3) Washing the cellulose gel electrolyte prepared in the step (2) with deionized water to be neutral, then soaking the cellulose gel electrolyte in acetonitrile solution of potassium iodide and iodine, wherein the concentration of the potassium iodide is 0.06mol/L, the concentration of the iodine is 0.03mol/L, and obtaining KI/I after 16 hours2Cellulose gel electrolyte (XWD-KI/I)2)。
Example 11
(1) Adding 1g of natural cellulose into 5mL of sodium hydroxide solution with the mass fraction of 30%, uniformly dispersing, then preserving heat for 20min at 28 ℃, then adding 2mL of carbon disulfide, reacting for 50min, adding 10mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 6, mixing, uniformly stirring, standing and crosslinking for 60 hours to obtain the cellulose gel electrolyte (XWD).
(3) Washing the cellulose gel electrolyte prepared in the step (2) with deionized water to be neutral, then soaking the cellulose gel electrolyte in acetonitrile solution of potassium iodide and iodine, wherein the concentration of the potassium iodide is 0.08mol/L, and the concentration of the iodine is 0.04mol/L), and obtaining KI/I after 18 hours2Cellulose gel electrolyte (XWD-KI/I)2)。
Example 12
(1) Adding 1g of natural cellulose into 6mL of sodium hydroxide solution with the mass fraction of 40%, uniformly dispersing, firstly preserving the temperature for 30min at the temperature of 30 ℃, then adding 2.5mL of carbon disulfide, reacting for 60min, adding 12mL of sodium hydroxide solution with the mass fraction of 4% after the product is converted into an orange solid state, and stirring for 20min until the product is completely uniform orange viscose.
(2) Mixing the viscose liquid prepared in the step (1) and deionized water according to a weight ratio of 1: 9, mixing, stirring uniformly, standing and crosslinking for 72 hours to obtain the cellulose gel electrolyte (XWD).
(3) Washing the cellulose gel electrolyte prepared in the step (2) with deionized water to be neutral, then soaking the cellulose gel electrolyte in acetonitrile solution of potassium iodide and iodine, wherein the concentration of the potassium iodide is 0.1mol/L, and the concentration of the iodine is 0.05mol/L), and obtaining KI/I after 24 hours2Cellulose gel electrolyte (XWD-KI/I)2)。

Claims (4)

1. A cellulose gel electrolyte material characterized by: the cellulose gel electrolyte material is prepared by using wood pulp, paper pulp, bamboo pulp or absorbent cotton which is made of natural cellulose as raw materials, reacting the raw materials with sodium hydroxide and carbon disulfide to synthesize cellulose viscose, and forming gel through hydration treatment, wherein the preparation method comprises the following steps:
(1) adding natural cellulose into a sodium hydroxide solution with the mass fraction of 16-40% according to the proportion of adding 3-6mL of the sodium hydroxide solution into each gram of natural cellulose, after the natural cellulose is uniformly dispersed, firstly, preserving the heat for 10-30min at the temperature of 25-30 ℃, then adding carbon disulfide into each gram of natural cellulose according to the proportion of adding 1-2.5mL of the carbon disulfide, reacting for 30-60min, after the natural cellulose is converted into an orange solid state, adding the sodium hydroxide solution with the mass fraction of 4% according to the proportion of adding 6-12mL of the sodium hydroxide solution into each gram of natural cellulose, and stirring until the natural cellulose completely becomes uniform orange viscose;
(2) and (2) mixing the viscose liquid prepared in the step (1) with deionized water according to the weight ratio of 1:1-9, uniformly stirring, standing and crosslinking for 48-72 hours to obtain the cellulose gel electrolyte (XWD).
2. A method for producing a cellulose gel electrolyte material according to claim 1, characterized in that:
(1) adding natural cellulose into a sodium hydroxide solution with the mass fraction of 16-40% according to the proportion of adding 3-6mL of the sodium hydroxide solution into each gram of natural cellulose, after the natural cellulose is uniformly dispersed, firstly, preserving the heat for 10-30min at the temperature of 25-30 ℃, then adding carbon disulfide into each gram of natural cellulose according to the proportion of adding 1-2.5mL of the carbon disulfide, reacting for 30-60min, after the natural cellulose is converted into an orange solid state, adding the sodium hydroxide solution with the mass fraction of 4% according to the proportion of adding 6-12mL of the sodium hydroxide solution into each gram of natural cellulose, and stirring until the natural cellulose completely becomes uniform orange viscose; the natural cellulose is paper pulp, wood pulp, bamboo pulp or absorbent cotton;
(2) and (2) mixing the viscose liquid prepared in the step (1) with deionized water according to the weight ratio of 1:1-9, uniformly stirring, standing and crosslinking for 48-72 hours to obtain the cellulose gel electrolyte (XWD).
3. The method for producing a cellulose gel electrolyte material according to claim 2, characterized in that: mixing the viscose liquid prepared in the step (1), potassium ferrocyanide and deionized water according to the weight ratio of 1:0.1-0.4:1-9, uniformly stirring, standing and crosslinking for 48-72 hours to obtain the potassium ferrocyanide-cellulose gel electrolyte (XWD-K)4[Fe(CN)6])。
4. The method for producing a cellulose gel electrolyte material according to claim 2, characterized in that: washing the cellulose gel electrolyte (XWD) prepared in the step (2) with deionized water to be neutral, then soaking the washed cellulose gel electrolyte (XWD) in acetonitrile solution of potassium iodide and iodine, wherein the concentration of the potassium iodide is 0.02-0.1mol/L, the concentration of the iodine is 0.01-0.05mol/L, and obtaining KI/I after 12-24 hours2Cellulose gel electrolyte (XWD-KI/I)2)。
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