CN109616650A - A kind of negative electrode material, preparation method and sodium-ion battery and its application using it - Google Patents
A kind of negative electrode material, preparation method and sodium-ion battery and its application using it Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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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- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/624—Electric conductive fillers
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of negative electrode material, preparation method and sodium-ion batteries and its application using it, and the negative electrode material includes nano-carbon material and the conjugated carbonyl compound that is supported on nano-carbon material, and the nano-carbon material is three dimensional skeletal structure；Negative electrode material improves the electric conductivity and high rate performance of electrode；The preparation method of negative electrode material is simple, and raw material is easy to get, cheap；Sodium-ion battery coulombic efficiency for the first time, high rate performance and cycle performance with higher are expected to be applied to industrial production.
Description
Technical field
The invention belongs to field of batteries, it is related to a kind of negative electrode material, preparation method and the sodium-ion battery using it
And its application.
Background technique
Clean energy resource, intelligent power grid technology development need a large amount of electric energy are temporarily stored, to extensive energy storage skill
The demand of art is increasingly urgent to.It is extensive energy storage system most potential at present by the secondary battery system of representative of lithium ion battery
System solution.But lithium resource reserves are limited, when rapid growth occurs for demand, the sensibility of supply and the constraint of geographical distribution
Property will cause the larger fluctuation of lithium price.Sodium have with physics similar in lithium and chemical property, go out from the sustainability of resource
Hair, reserves sodium resource more abundant provide better choice for the development of sustainability electrochemical energy storage technology.In addition, sodium
Ion battery also has expected cost more lower than lithium ion battery, comprehensive resources sustainability and cost factor, sodium ion electricity
Application of the pond more suitable for large-scale energy storage system.
Lower energy density is the significant challenge for limiting sodium-ion battery functionization.In order to improve sodium-ion battery energy
Density needs to develop the negative electrode material with height ratio capacity, lower oxidation reduction potential and quick deintercalation sodium ion performance.Sodium ion
Diameter is greater than lithium ion, and the insertion and abjection process dynamics in conventional lithium ion negative electrode material are much more slowly than lithium ion；Together
When, the deintercalation process of sodium ion will generate bigger volume change, and the requirement to electrode material anti-aging property is also more stringent.
Theory analysis discovery, using alloy, metal oxide, metal sulfide and metal phosphide as negative electrode material, is expected to obtain
With sodium-ion battery similar in commercial li-ion battery energy density.However such inorganic electrode material is greatly mostly from can not be again
Raw mineral extract, extraction process would generally use toxic chemical and strong acid, and electrode material recovery difficult is big, material
The environment of Life cycle influences higher.In order to apply to large-scale energy storage system, need to develop green, sustainable electrode
Material.
Organic electrode materials have the spy that structure is adjustable, height ratio capacity and dynamic process are insensitive to embedded ion radius
Point, and low energy consumption for organic electrode materials synthesis technology, and is easier to be recycled by low-temperature burning process, is a kind of ideal
Green, sustainable electrode material suitable for extensive battery system.But since organic material is easy in common electrolyte
Middle to dissolve, storage sodium process dynamics is relatively slow, and material sheet is lower as insulator or conductivity, needs in practical process
A large amount of conductive agent is added, the energy density of electrode is reduced, also limits the practical application of organic electrode materials.
Application study of the conjugated carbonyl compound in sodium-ion battery cathode is relatively broad, wherein disodium terephthalate
(Na2C8H4O4, Na2TP) it is organic compound that the first is applied in sodium-ion battery cathode.Na2TP is with higher reversible
Specific capacity, preferable cyclical stability, and since the biggish polarity of carboxylate makes it insoluble in common organic electrolyte.
Zhao etc. (Adv.Energy Mater.2012,2,962) is by the method for ball milling by commercial Na2TP is mixed with Ketjen black
Cathode reports Na for the first time2Application of the TP in sodium-ion battery.It is observed in electrochemical Characterization, Na2There are one for TP material
A sodium ion positioned at 0.29V is embedded in voltage platform and a sodium ion deintercalation voltage platform for being located at 0.56V, the material can
Inverse capacity is 250mAh/g.But the larger irreversible capacity of bring makes the first circle coulombic efficiency of battery only due to SEI formation
It is 50.3%.In order to solve this problem, Zhao etc. by the method for ALD in electrode material surface coated aluminum oxide, by subtracting
Slow electrolyte reduces irreversible capacity in the decomposition of electrode surface, successfully by battery first circle coulombic efficiency improve to 60% with
On.Meanwhile the processing of ALD cladding further improves the circulation and high rate performance of electrode.Park etc. (Adv.Mater.2012,24,
3562) Na is prepared for using the method for recrystallization2TP, and have studied Na2TP and its amino, bromo and nitro substituent sodium from
Application in sub- battery cathode.Other functional groups are introduced by the position of facing in carboxyl, Park etc. has found the heat of organic electrode materials
Mechanics and kinetic property simply can be realized very by chemical modification.For example, by converting thio carboxylic for carboxylate
Hydrochlorate can get better specific capacity, can obtain higher average voltage by the way that phenyl ring is carried out p doping, be organic electrode material
The successful application of material in the secondary battery provides possibility.However, Na2TP is almost non-conductive, in electrode production process often
Needing to be added beyond the conductive additive of 40% mass ratio, this undoubtedly will be greatly reduced the mass energy density of battery device, and
And conductive additive can also cause a large amount of irreversible reaction in charge and discharge process.
CN107293736A discloses a kind of sodium-ion battery negative electrode material, including granules of stannic oxide and is embedded in described
The titanium oxide spherical nanoparticle of granules of stannic oxide, the inlay of the granules of stannic oxide and the titanium oxide spherical nanoparticle
It is divided into the Particles dispersed of Nano grade, the diameter of the titanium oxide spherical nanoparticle is 2nm 200nm；This aspect preparation is born
Pole material has preferable cyclical stability and capacity, but its electrode material recovery difficult is big, is unfavorable for environmental protection.
CN108899211A discloses a kind of sodium ion capacitor and its system for having both high-energy density and high power density
Preparation Method belongs to sodium ion capacitor technology field, which is negative with molybdenum disulfide/graphene composite material
Pole, porous carbon materials are anode；The sodium ion capacitor charge/discharge capacity with higher and speed of invention preparation, but its
Chemical property is still to be improved.
Therefore, develop it is a kind of conduct electricity very well, energy density is high, high rate performance is excellent, good cycling stability negative electrode material
It is highly desirable.
Summary of the invention
The purpose of the present invention is to provide a kind of negative electrode material, preparation method and using it sodium-ion battery and its
Using the negative electrode material improves the electric conductivity and high rate performance of electrode, and the preparation method of negative electrode material is simple, and raw material is easy
, the sodium-ion battery coulombic efficiency for the first time, high rate performance and cycle performance with higher are expected to be applied to industry life
It produces.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of negative electrode material, the negative electrode material includes nano-carbon material and attachment
Conjugated carbonyl compound on nano-carbon material, the nano-carbon material are three dimensional skeletal structure.
Negative electrode material electric conductivity, first circle coulombic efficiency and specific capacity with higher of the present invention, have simultaneously
Preferable cyclical stability and high rate performance.
Conjugated carbonyl compound (i.e. carbonyl and other groups are conjugated) uniform load is in the carbon materials of three-dimensional framework in the present invention
On material, the electric conductivity of electrode is substantially increased, and pore structure abundant for ion transport provides channel in electrode, is conducive to
Improve the high rate performance of electrode.
Nano-carbon material is three dimensional skeletal structure in the present invention, further increases the electric conductivity and stable circulation of electrode
Property.
In the present invention, the nano-carbon material includes in graphene, carbon nanotube, nano carbon fiber or conductive carbon black
It is one of or at least two combination, preferred graphene.
In the present invention, nano-carbon material is three dimensional skeletal structure, specific surface area and porosity with higher, convenient for improving
The electric conductivity and high rate performance of negative electrode material.
In the present invention, the conjugated carbonyl compound includes any one in carboxylate, quinones organic matter or polyimides
Kind or at least two combination, preferred carboxylate.
In the present invention, the carboxylate is dithionate.
In the present invention, the carboxylate is terephthalate, preferably disodium terephthalate.
Conjugated carbonyl compound reversible specific capacity with higher and cyclical stability in the present invention, and due to higher
Polarity makes it insoluble in conventional electrolysis liquid, can increase the security performance of battery.
In the present invention, the partial size of the conjugated carbonyl compound be 1-1000nm, such as 1nm, 10nm, 50nm,
100nm、150nm、200nm、250nm、300nm、350nm、400nm、450nm、500nm、600nm、700nm、800nm、
900nm, 1000nm etc..
The partial size of conjugated carbonyl compound is 1-1000nm in the present invention, and in the range, the electrode material of preparation has
Preferable high rate performance, when partial size is excessively high, then high rate performance can be poor, when partial size is too low, then side reaction, shadow can occur
Ring the performance of electrode material.
In the present invention, the specific surface area of the conjugated carbonyl compound is 20-30m2/ g, such as 20m2/g、22m2/g、
24m2/g、25m2/g、26m2/g、28m2/g、30m2/ g etc..
The specific surface area of conjugated carbonyl compound is 20-30m in the present invention2/ g, the electrode material prepared in the range
Capacity and cyclical stability with higher；When the specific surface area of conjugated carbonyl compound is too low, the capacity of electrode material compared with
It is low；When the specific surface area of conjugated carbonyl compound is excessively high, the cyclical stability of electrode material can be reduced.
In the present invention, the mass ratio of the conjugated carbonyl compound and nano-carbon material be 4:1-16:1, such as 4:1,
5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1,13:1,14:1,15:1,16:1 etc..
In the present invention, the mass ratio of conjugated carbonyl compound and nano-carbon material is 4:1-16:1, in the range, preparation
Negative electrode material circulation with higher and high rate performance, and only can meet higher conduction with less amount of conductive agent is added
Performance；When the mass ratio of the two is lower than 4:1, although can achieve higher reversible specific capacity and circulation conservation rate, meeting is big
The big high rate performance for reducing electrode material；When the mass ratio of the two is excessively high, although having preferable cycle performance and high rate performance,
But it needs to be added a large amount of conductive additive and is just able to satisfy preferable electric conductivity, but a large amount of conductive additive is added
The energy density of electrode can be reduced, while can also cause a large amount of irreversible reaction in charge and discharge process again to reduce the coulomb of battery
Efficiency.
The second object of the present invention is to provide a kind of preparation method of negative electrode material, and the preparation method includes following step
It is rapid:
(1) conjugated carbonyl compound solution and nano-carbon material dispersion liquid are mixed, obtains mixed liquor；
(2) mixed liquor that step (1) is prepared successively is freezed, dried, be heat-treated, obtain the negative electrode material.
The preparation method that the present invention prepares negative electrode material is simple, and raw material is easy to get, and can be expected to be applied to industrial production.
In the present invention, the preparation method of step (1) the conjugated carbonyl compound solution includes: to close conjugated carbonyl
Object is dissolved in solvent, obtains the conjugated carbonyl compound solution.
In the present invention, the solvent is any one in water, ethyl alcohol or N-Methyl pyrrolidone or at least two
Combination, preferably water.
In the present invention, the preparation method of step (1) described nano-carbon material dispersion liquid includes: to disperse nano-carbon material
In dispersing agent, the nano-carbon material dispersion liquid is obtained.
In the present invention, the dispersing agent is any one in water, ethyl alcohol or N-Methyl pyrrolidone or at least two
Combination, preferred water.
In the present invention, the mode of the dispersion is ultrasonic disperse.
In the present invention, the jitter time is 1-4h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h etc..
It in the present invention by the way of ultrasonic disperse, can be uniformly dispersed, be altogether in a solvent convenient for nano-carbon material
When yoke carbonyls solution mixes, convenient for conjugated carbonyl compound uniform load on nano-carbon material.
In the present invention, step (1) the mixed mode is stirring or ultrasound.
In the present invention, step (2) freezing is to freeze in liquid nitrogen environment.
In the present invention, step (2) drying is vacuum freeze drying.
Vacuum freeze drying is used in the present invention, i.e., mixed liquor is kept into the solid-state after freezing at a lower temperature, then
Moisture therein is directly sublimed into gaseous state without liquid under vacuum condition again, convenient for keeping the three-dimensional framework knot of nano-carbon material
Structure.
In the present invention, the pressure of the vacuum freeze drying be 1.3-13Pa, such as 1.3Pa, 2Pa, 3Pa, 4Pa,
5Pa, 6Pa, 7Pa, 8Pa, 9Pa, 10Pa, 11Pa, 12Pa, 13Pa etc..
In the present invention, the temperature of the vacuum freeze drying is -50 DEG C~-10 DEG C, such as -50 DEG C, -45 DEG C, -40
DEG C, -35 DEG C, -30 DEG C, -25 DEG C, -20 DEG C, -15 DEG C, -10 DEG C etc..
In the present invention, the temperature of step (2) described heat treatment be 200-500 DEG C, such as 200 DEG C, 250 DEG C, 300 DEG C,
350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C etc..
In the present invention, step (2) heat treatment is carried out under reducibility gas and/or protective gas.
In the present invention, the reducibility gas is hydrogen.
In the present invention, the protective gas includes any one in nitrogen, argon gas or helium or at least two
Combination.
As the preferred technical solution of the application, the preparation process includes the following steps:
(1) conjugated carbonyl compound is dissolved in solvent, the conjugated carbonyl compound solution is obtained, by nano-carbon material
It is dispersed in dispersing agent in a manner of ultrasonic disperse, jitter time 1-4h obtains the nano-carbon material dispersion liquid, then will
Obtained conjugated carbonyl compound solution and nano-carbon material dispersion liquid, stirring or ultrasound, obtain mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 1.3- in the pressure of vacuum
13Pa, temperature is vacuum freeze drying under conditions of -50 DEG C~-10 DEG C, finally under reducibility gas and/or protective gas
It is heat-treated, the temperature of heat treatment is 200-500 DEG C, obtains the negative electrode material.
The third object of the present invention is to provide a kind of sodium-ion battery, the sodium-ion battery include electrolyte, diaphragm,
Anode and cathode, one of for the purpose of the negative electrode material in the cathode described in negative electrode material.
In the present invention, the positive electrode in the anode is sodium sheet metal.
In the present invention, the diaphragm is any one in glass fibre, PP or PE.
In the present invention, the electrolyte includes electrolyte and organic solvent.
In the present invention, the electrolyte is trifluoromethyl sulfonate and/or sodium hexafluoro phosphate.
In the present invention, the organic solvent is straight chain ethers；
In the present invention, the organic solvent includes diethylene glycol dimethyl ether, glycol dimethyl ether or tetraethylene glycol diformazan
In ether any one or at least two combination.
The fourth object of the present invention is to provide a kind of sodium-ion battery as described in the third purpose and answers as power battery
For in electric car.
Compared with the existing technology, the invention has the following advantages:
On the one hand the present invention can increase leading for negative electrode material by loading conjugated carbonyl compound on nano-carbon material
Electrical property provides channel for the transmission of ion, cathode can be improved on the other hand due to being rich in pore structure in nano-carbon material
The high rate performance of material；Nano-carbon material is three dimensional skeletal structure, can further increase the electric conductivity and stable circulation of electrode
Property；The preparation method of negative electrode material is simple, and raw material is easy to get, cheap, is expected to be used for industrialized production；With the cathode material of preparation
Material is (first discharge specific capacity is up to applied to the first discharge specific capacity that in sodium-ion battery, can increase sodium-ion battery
340mAh/g), coulombic efficiency (coulombic efficiency is up to 92% for the first time), high rate performance (capacity under 2A/g current density for the first time
115mAh/g) and cyclical stability (circulation 200 circle after capacity up to 232mAh/g).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the negative electrode material prepared in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of negative electrode material prepared by the embodiment of the present invention 1, and scale is 5 μm；
Fig. 3 is the isothermal nitrogen adsorption desorption curve of negative electrode material prepared by the embodiment of the present invention 1；
Fig. 4 is the preceding two circles discharge curve of negative electrode material prepared by the embodiment of the present invention 1；
Fig. 5 is the multiplying power and cycle performance curve of negative electrode material prepared by the embodiment of the present invention 1.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of negative electrode materials, as shown in Figure 1, negative electrode material described in the negative electrode material includes nano-sized carbon
Material and the conjugated carbonyl compound being attached on nano-carbon material, the nano-carbon material are three dimensional skeletal structure；Wherein receive
Rice carbon material is graphene；Conjugated carbonyl compound is disodium terephthalate；The partial size of disodium terephthalate is 500nm,
Specific surface area is 25m2/g；The mass ratio of conjugated carbonyl compound and nano-carbon material is 10:1.
The preparation method of the negative electrode material includes:
(1) 400mg disodium terephthalate is dissolved in 1mL deionized water, obtains the disodium terephthalate solution,
40mg graphene oxide is added in 20mL deionized water, ultrasonic disperse 2h obtains the graphene oxide dispersion, then
The disodium terephthalate solution and graphene oxide dispersion that will be obtained, stirring, obtain mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 10Pa in the pressure of vacuum,
Temperature is vacuum freeze drying under conditions of -44 DEG C, is finally heat-treated under reducibility gas and/or protective gas,
The temperature of heat treatment is 450 DEG C, obtains the negative electrode material.
Fig. 2 is the scanning electron microscope (SEM) photograph of negative electrode material prepared by the embodiment of the present invention 1, and scale is 5 μm, figure it is seen that
Disodium terephthalate is evenly distributed on redox graphene lamella.
Fig. 3 is the isothermal nitrogen adsorption desorption curve of negative electrode material prepared by the embodiment of the present invention 1, as can be seen from Figure 3
The specific surface area numerical value of electrode material is only 25m2/ g, low specific surface area advantageously reduce the generation of side reaction, promote electrode
The initial coulomb efficiency of material.
Fig. 4 is the preceding two circles discharge curve of negative electrode material prepared by the embodiment of the present invention 1, as can be seen from Figure 4 this electrode
The specific discharge capacity of material is about 300mAh/g, has longer platform in 0.25V or so, can be to avoid the deposition of lithium metal, phase
Than in traditional carbon electrode material, there is better security performance.
Fig. 5 is the multiplying power and cycle performance curve graph of negative electrode material prepared by the embodiment of the present invention 1, as can be seen from Figure 5
Negative electrode material manufactured in the present embodiment has excellent high rate performance and cyclical stability.
Embodiment 2
The present embodiment provides a kind of negative electrode material, negative electrode material described in the negative electrode material includes nano-carbon material and load
Conjugated carbonyl compound on nano-carbon material, the nano-carbon material are three dimensional skeletal structure；Wherein nano-carbon material is
Carbon nanotube；Conjugated carbonyl compound is polyimides；The partial size of polyimides is 200nm, specific surface area 20m2/g；Conjugation
The mass ratio of carbonyls and nano-carbon material is 6:1.
The preparation method of the negative electrode material includes:
(1) 240mg polyimides is dissolved in 1mL ethyl alcohol, obtains the polyimide solution, 40mg carbon nanotube is added
Enter into 20mL ethyl alcohol, ultrasonic disperse 1h obtains the carbon nano tube dispersion liquid, then by obtained polyimide solution and carbon
Nanotube dispersion liquid, stirring, obtains mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 1.3Pa in the pressure of vacuum,
Temperature is vacuum freeze drying under conditions of -50 DEG C, is finally heat-treated under reducibility gas and/or protective gas,
The temperature of heat treatment is 200 DEG C, obtains the negative electrode material.
Embodiment 3
The present embodiment provides a kind of negative electrode material, negative electrode material described in the negative electrode material includes nano-carbon material and load
Conjugated carbonyl compound on nano-carbon material, the nano-carbon material are three dimensional skeletal structure；Wherein nano-carbon material is
Nano carbon fiber；Conjugated carbonyl compound is cyclohexadiene diketone；The partial size of cyclohexadiene diketone is 800nm, and specific surface area is
30m2/g；The mass ratio of conjugated carbonyl compound and nano-carbon material is 14:1.
The preparation method of the negative electrode material includes:
(1) 560mg cyclohexadiene diketone is dissolved in 1mL ethyl alcohol, obtains the cyclohexadiene diketone solution, 40mg is received
Rice Carbon fibe is added in 20mL ethyl alcohol, and ultrasonic disperse 4h obtains the nano carbon fiber dispersion liquid, the hexamethylene that will then obtain
Diene diketone solution and nano carbon fiber dispersion liquid, stirring, obtain mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 13Pa in the pressure of vacuum,
Temperature is vacuum freeze drying under conditions of -10 DEG C, is finally heat-treated under reducibility gas and/or protective gas,
The temperature of heat treatment is 500 DEG C, obtains the negative electrode material.
Embodiment 4
The present embodiment provides a kind of negative electrode material, negative electrode material described in the negative electrode material includes nano-carbon material and load
Conjugated carbonyl compound on nano-carbon material, the nano-carbon material are three dimensional skeletal structure；Wherein nano-carbon material is
Conductive carbon black；Conjugated carbonyl compound is carbodithioic acid sodium；The partial size of carbodithioic acid sodium is 1000nm, and specific surface area is
30m2/g；The mass ratio of conjugated carbonyl compound and nano-carbon material is 4:1.
The preparation method of the negative electrode material includes:
(1) 160mg carbodithioic acid sodium is dissolved in 1mL deionized water, obtains the carbodithioic acid sodium solution, it will
40mg conductive carbon black is added in 20mL deionized water, ultrasonic disperse 4h, is obtained the conductive black dispersion liquid, will then be obtained
Carbodithioic acid sodium solution and conductive black dispersion liquid, stirring, obtain mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 2Pa, temperature in the pressure of vacuum
Degree is vacuum freeze drying under conditions of -30 DEG C, is finally heat-treated under reducibility gas and/or protective gas, heat
The temperature of processing is 400 DEG C, obtains the negative electrode material.
Embodiment 5
The present embodiment provides a kind of negative electrode material, negative electrode material described in the negative electrode material includes nano-carbon material and load
Conjugated carbonyl compound on nano-carbon material, the nano-carbon material are three dimensional skeletal structure；Wherein nano-carbon material is
Conductive carbon black；Conjugated carbonyl compound is disodium terephthalate；The partial size of disodium terephthalate is 1nm, and specific surface area is
20m2/g；The mass ratio of disodium terephthalate and conductive carbon black is 16:1.
The preparation method of the negative electrode material includes:
(1) 640mg disodium terephthalate is dissolved in 1mL deionized water, obtains the disodium terephthalate solution,
40mg conductive carbon black is added in 20mL deionized water, ultrasonic disperse 2h, obtains the conductive black dispersion liquid, then incited somebody to action
The disodium terephthalate solution and conductive black dispersion liquid arrived, stirring, obtains mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 10Pa in the pressure of vacuum,
Temperature is vacuum freeze drying under conditions of -20 DEG C, is finally heat-treated under reducibility gas and/or protective gas,
The temperature of heat treatment is 300 DEG C, obtains the negative electrode material.
Embodiment 6
Difference with embodiment is only that the partial size of conjugated carbonyl compound is 0.1nm, remaining raw material and preparation method thereof
It is same as Example 1.
Embodiment 7
Difference with embodiment is only that the partial size of conjugated carbonyl compound is 2000nm, remaining raw material and preparation method thereof
It is same as Example 1.
Embodiment 8
Difference with embodiment is only that the specific surface area of conjugated carbonyl compound is 10m2/ g, remaining raw material and its preparation
Method is same as Example 1.
Embodiment 9
Difference with embodiment is only that the specific surface area of conjugated carbonyl compound is 50m2/ g, remaining raw material and its preparation
Method is same as Example 1.
Embodiment 10
Difference with embodiment is only that the mass ratio of conjugated carbonyl compound and nano-carbon material is 1:1, remaining raw material
And preparation method thereof it is same as Example 1.
Embodiment 11
Difference with embodiment is only that the mass ratio of conjugated carbonyl compound and nano-carbon material is 30:1, remaining raw material
And preparation method thereof it is same as Example 1.
Comparative example 1
Difference with embodiment 1 is only that the nano-carbon material is non-three dimensional skeletal structure, remaining is former without processing
Material and preparation method thereof is same as Example 1.
Comparative example 2
Difference with embodiment 1 is only that the negative electrode material does not include conjugated carbonyl compound, remaining raw material and its system
Preparation Method is same as Example 1.
Comparative example 3
Difference with embodiment 1 is only that carbonyls is that (i.e. carbonyl and other groups be not total to phenylenediacetic Acid sodium
Yoke), remaining raw material and preparation method thereof is same as Example 1.
Comparative example 4
Difference with embodiment 1 is only that conjugated compound is paraxylene (i.e. without carbonyl), remaining raw material and its system
Preparation Method is same as Example 1.
Negative electrode material prepared by embodiment 1-11 and comparative example 1-4 carries out electrochemical property test:
Electro-chemical test:
(1) preparation of sodium-ion battery: the negative electrode material being prepared is prepared into negative electrode tab, metallic sodium piece is as just
Pole, diaphragm are glass fibre, and electrolyte is sodium hexafluoro phosphate in electrolyte, organic solvent is diethylene glycol dimethyl ether, are assembled into
Button cell.
(2) first discharge specific capacity: using the electrochemistry of blue electricity 5V/2mA type cell tester test battery
Performance, charge and discharge window are 0.005V~2.0V, charge-discharge velocity 50mAh/g.
(3) chemical property of battery, charge and discharge coulombic efficiency for the first time: are tested using blue electricity 5V/2mA type cell tester
Window is 0.005V~2.0V, charge-discharge velocity 50mAh/g, and coulombic efficiency=initial charge specific capacity/discharges for the first time for the first time
Specific capacity.
(4) cycle performance: using the chemical property of blue electricity 5V/2mA type cell tester test battery, charge and discharge window
For 0.005V~2.0V, charge-discharge velocity 50mAh/g, circulating ring number is 200 circles.
(5) high rate performance is tested: using the chemical property of blue electricity 5V/10mA type cell tester test battery, charge and discharge
Electric window is 0.005V~2.0V, and charge-discharge velocity is respectively 50mAh/g, 100mAh/g, 200mAh/g, 500mAh/g, 1Ah/
G, 2Ah/g, 5Ah/g, circulating ring number is 5 circles under every kind of charge-discharge velocity.
Test result is shown in Table 1:
Table 1
The cycle performance is the capacity (mAh/g) recycled after 200 circles；
The high rate performance is capacity (mAh/g) under 2A/g current density.
As shown in Table 1, negative electrode material prepared by the present invention has preferable chemical property；By embodiment 1-5 and implementation
The comparison of example 6 is it is found that when the partial size of conjugated carbonyl compound is lower than the sodium ion electricity within the framework of the present definition, then prepared
The coulombic efficiency for the first time and cycle performance in pond can decrease；By the comparison of embodiment 1-5 and embodiment 7 it is found that when conjugation carbonyl
The partial size of based compound is higher than within the framework of the present definition, then the first discharge specific capacity of the sodium-ion battery prepared has
It is reduced；By the comparison of embodiment 1-5 and embodiment 8 it is found that when the specific surface area of conjugated carbonyl compound is lower than present invention limit
Within the scope of fixed, then the first discharge specific capacity and cycle performance of the sodium-ion battery prepared can reduce；By embodiment 1-5 and
The comparison of embodiment 9 is then prepared it is found that when the specific surface area of conjugated carbonyl compound is higher than within the framework of the present definition
Sodium-ion battery high current discharge capacity and cycle performance can reduce；It can by the comparison of embodiment 1-5 and embodiment 10
Know, when the mass ratio of conjugated carbonyl compound and nano-carbon material lower than the sodium within the framework of the present definition, then prepared from
The discharge capacity of the discharge capacity for the first time of sub- battery, for the first time coulombic efficiency, cycle performance and high current can decrease；By reality
The comparison of a 1-5 and embodiment 11 is applied it is found that when the mass ratio of conjugated carbonyl compound and nano-carbon material is higher than present invention limit
Within the scope of fixed, then the discharge capacity and cycle performance of the high current of the sodium-ion battery prepared can decrease；By reality
The comparison of example 1 and comparative example 1 is applied it is found that when nano-carbon material is non-three dimensional skeletal structure, the then property of the sodium-ion battery prepared
It can will be greatly reduced；By the comparison of embodiment 1 and comparative example 2 it is found that when not including conjugated carbonyl compound in negative electrode material,
Although the first discharge specific capacity of the sodium-ion battery of preparation is higher, its coulombic efficiency, cycle performance and forthright again for the first time
It can substantially reduce；By the comparison of embodiment 1 and comparative example 3 it is found that when carbonyls be non-conjugated structure, then the sodium prepared from
The performance of sub- battery will be greatly reduced；By the comparison of embodiment 1 and comparative example 4 it is found that when not including carbonyl in conjugated compound,
The performance of the sodium-ion battery then prepared will be greatly reduced, influence using；Therefore, negative electrode material prepared by the present invention has preferable
First discharge specific capacity, the discharge capacity of coulombic efficiency, cycle performance and high current for the first time.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of negative electrode material, which is characterized in that the negative electrode material includes nano-carbon material and is attached on nano-carbon material
Conjugated carbonyl compound, the nano-carbon material be three dimensional skeletal structure.
2. negative electrode material according to claim 1, which is characterized in that the nano-carbon material includes graphene, carbon nanometer
In pipe, nano carbon fiber or conductive carbon black any one or at least two combination, preferred graphene.
3. negative electrode material according to claim 1 or 2, which is characterized in that the conjugated carbonyl compound include carboxylate,
Any one in quinones organic matter or polyimides or at least two combination, preferred carboxylate；
Preferably, the carboxylate is dithionate；
Preferably, the carboxylate is terephthalate, preferably disodium terephthalate.
4. negative electrode material according to claim 1-3, which is characterized in that the partial size of the conjugated carbonyl compound
For 1-1000nm；
Preferably, the specific surface area of the conjugated carbonyl compound is 20-30m2/g；
Preferably, the mass ratio of the conjugated carbonyl compound and nano-carbon material is 4:1-16:1.
5. the preparation method of negative electrode material according to claim 1-4, which is characterized in that the preparation method packet
Include following steps:
(1) conjugated carbonyl compound solution and nano-carbon material dispersion liquid are mixed, obtains mixed liquor；
(2) mixed liquor that step (1) is prepared successively is freezed, dried, be heat-treated, obtain the negative electrode material.
6. preparation method according to claim 5, which is characterized in that step (1) the conjugated carbonyl compound solution
Preparation method includes: that conjugated carbonyl compound is dissolved in solvent, obtains the conjugated carbonyl compound solution；
Preferably, the solvent be water, ethyl alcohol or N-Methyl pyrrolidone in any one or at least two combination, preferably
Water；
Preferably, the preparation method of step (1) described nano-carbon material dispersion liquid includes: that nano-carbon material is dispersed in dispersing agent
In, obtain the nano-carbon material dispersion liquid；
Preferably, the dispersing agent be water, ethyl alcohol or N-Methyl pyrrolidone in any one or at least two combination, it is excellent
Select water；
Preferably, the mode of the dispersion is ultrasonic disperse；
Preferably, the jitter time is 1-4h；
Preferably, step (1) the mixed mode is stirring or ultrasound.
7. preparation method according to claim 5 or 6, which is characterized in that step (2) freezing is in liquid nitrogen environment
Freezing；
Preferably, step (2) drying is vacuum freeze drying；
Preferably, the pressure of the vacuum freeze drying is 1.3-13Pa；
Preferably, the temperature of the vacuum freeze drying is -50 DEG C~-10 DEG C；
Preferably, the temperature of step (2) described heat treatment is 200-500 DEG C；
Preferably, step (2) heat treatment is carried out under reducibility gas and/or protective gas；
Preferably, the reducibility gas is hydrogen；
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination.
8. according to the described in any item preparation methods of claim 4-6, which is characterized in that the preparation process includes following step
It is rapid:
(1) conjugated carbonyl compound is dissolved in solvent, obtains the conjugated carbonyl compound solution, by nano-carbon material with super
The mode of sound dispersion is dispersed in dispersing agent, and jitter time 1-4h obtains the nano-carbon material dispersion liquid, will then obtain
Conjugated carbonyl compound solution and nano-carbon material dispersion liquid, stirring or ultrasound, obtain mixed liquor；
(2) mixed liquor that step (1) is prepared is freezed in liquid nitrogen environment, is then 1.3-13Pa in the pressure of vacuum,
Temperature is vacuum freeze drying under conditions of -50 DEG C~-10 DEG C, is finally carried out under reducibility gas and/or protective gas
Heat treatment, the temperature of heat treatment are 200-500 DEG C, obtain the negative electrode material.
9. a kind of sodium-ion battery, which is characterized in that the sodium-ion battery includes electrolyte, diaphragm, anode and cathode, described
Negative electrode material in cathode is the described in any item negative electrode materials of claim 1-4.
10. a kind of sodium-ion battery as claimed in claim 9 is applied in electric car as power battery.
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