CN110407193A - A kind of negative electrode material and preparation method thereof and the sodium-ion battery containing the negative electrode material - Google Patents
A kind of negative electrode material and preparation method thereof and the sodium-ion battery containing the negative electrode material Download PDFInfo
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- CN110407193A CN110407193A CN201910766292.2A CN201910766292A CN110407193A CN 110407193 A CN110407193 A CN 110407193A CN 201910766292 A CN201910766292 A CN 201910766292A CN 110407193 A CN110407193 A CN 110407193A
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- C01B32/00—Carbon; Compounds thereof
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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
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a kind of negative electrode material and preparation method thereof and contain the sodium-ion battery of the negative electrode material, the preparation method comprises the following steps: (1) preparing inorganic salt solution first, chitin or chitin derivativ powder is then added, it is slowly added to cosolvent, lasting stirring or ultrasound obtain uniform colloidal sol；(2) colloidal sol obtained by step (1) is freezed and is dried in vacuo to obtain fluffy presoma；(3) presoma obtained by step (2) is subjected to high-temperature calcination under an inert atmosphere, chitin or chitin derivativ utilize inorganic salts to melt evaporation characteristic, porous hard carbon material are made in situ during being carbonized.Negative electrode material of the invention has crosslinking hole configurations, and specific surface is big, rich Nitrogen element.The electronic conductance that ensure that material is high of abundant nitrogen, while three-dimensional crosslinked network is conducive to sodium ion in quick deintercalation wherein, realizes high capacity, the high rate charge-discharge of battery, improves the cyclical stability of battery.
Description
Technical field
The present invention relates to battery material fields, and in particular, to a kind of negative electrode material, the preparation method of the negative electrode material with
And the sodium-ion battery containing the negative electrode material.
Background technique
Traditional fossil energy such as coal, petroleum, natural gas etc. is increasingly exhausted and pollution on the environment is significant, into 21 generation
It records, the main problem of energy crisis and problem of environmental pollution as facing mankind.Devoting Major Efforts To Developing utilizes wind energy, the sun with efficient
The renewable and clean energy resources such as energy, tide energy, nuclear energy, geothermal energy, which become, solves the above-mentioned most effective approach of two large problems.Secondary electricity
Carrier of the pond as energy storage and conversion, carries the hope restructured the use of energy and reduced environmental pollution.
Although secondary cell can be used as energy storage and powering device preferably solves the problems, such as this.Wherein lithium ion battery has
Have the advantages that numerous such as energy densities are high, have extended cycle life, environmental nuisance is small, average output voltage is high, output power, from
Discharge small, memory-less effect etc..But due to being limited by resource, lithium ion battery cost is high.Sodium and lithiumation
Property is close, and sodium resource is nearly 400 times of lithium resource, and cost is only the 1/80 of lithium resource.Sodium is located at lithium simultaneously
Same main group, the current potential of sodium are -2.71V vs.SHE, and very close to-the 3.04V of lithium, chemical property is close, are its battery system
Foundation provide possibility.
In recent years, positive electrode studied in sodium ion battery electrode material more sufficiently, have stablize deintercalation sodium from
The positive electrode of son there are many, such as stratified material, polyanionic compound and Prussian blue similar object.However negative electrode material
In all various aspects still by various restrictions.Mainly there are carbon-based material, metal oxide/sulfide, conjunction in current negative electrode material
Aurification material, titanium base material etc..Wherein from the point of view of cost and cyclical stability, hard carbon material is used as sodium ion cathode
Material has apparent advantage.Hard carbon material is usually made of different carbon sources by high temperature cabonization, therefore the selection of carbon source
As wherein important component part.Chitin is one of reserves natural polymer the most abundant in nature, with honest and clean
Valence, easily obtains and the advantages such as recyclable.Therefore we select this kind of substance or derivatives thereof as carbon source, thus expand sodium from
The cheap advantage of sub- battery.
Usual porous carbon materials need to obtain using the reactive ion etching of highly basic and carbon at high temperature, such as most commonly used make
Hole agent KOH.This method application is wider, but have it is subsequent in strong corrosivity and this method also need a large amount of acid, it is right
Environment causes greatly to pollute.Currently, there is environmental-friendly pore forming material to be also gradually concerned, for example, NaCl is due to easily
It is dissolved in the water, is used as pore creating material, but in this process merely with the effect of its physics occupy-place, lower than below fusing point
The pore structure of NaCl preparation disperses and is single macropore.It is cleaned by ultrasonic etc. in subsequent process there is still a need for a large amount of water
Complicated step is played.Therefore a kind of method for finding extremely simple economy prepares cross-linked porous carbon negative pole material with important meaning
Justice.
Summary of the invention
The purpose of the present invention overcomes the shortcomings of existing pore forming material and preparation method thereof, provides and a kind of extremely simply prepares
Negative electrode material, the preparation method of the negative electrode material and the sodium-ion battery containing the negative electrode material.Negative electrode material of the invention
With three-dimensional crosslinked network shape structure, specific surface is big, and nitrogen interconnected and rich in, not only contributes between hole
Sodium ion quick deintercalation in the material, realizes high capacity, the high rate charge-discharge of battery, and the circulation that can be improved battery is steady
It is qualitative.
It was found by the inventors of the present invention that salting liquid is formed by the way that first inorganic salts are dissolved in deionized water, then at it
Middle addition chitin or chitin derivativ powder, uniformly rear addition cosolvent to be mixed.Lasting stirring is so that solution is in semi-transparent
Gelatin-like.Then the solution is transferred in low temperature environment and is freezed, to keep the original pattern of material.Keeping pattern
Under the premise of the moisture in material is dried, finally obtain fluffy bulk material.By the material in inert atmosphere protection
Lower high-temperature calcination.Three-dimensional porous network shape negative electrode material can be obtained without subsequent processing.By control solvent order of addition,
Calcination temperature, calcination time, and then the technologies such as melting and evaporation rate for controlling inorganic salts, so that material is shown by three-dimensional
The block structure that porous network is constituted.The special construction is not only that sodium ion transmission provides quick channel, and complete body
Block structure is also able to maintain extremely stable performance in cyclic process.And then realize high capacity, the high rate charge-discharge of battery,
Improve the cyclical stability of battery.
First aspect present invention provides a kind of method that porous hard carbon cathode material is prepared in situ in inorganic salts melting evaporation,
Wherein, it the described method comprises the following steps:
(1) inorganic salt solution is prepared first, and chitin or chitin derivativ powder is then added, is slowly added to hydrotropy
Agent, lasting stirring or ultrasound obtain uniform colloidal sol；
(2) colloidal sol obtained by step (1) is freezed and is dried in vacuo to obtain fluffy presoma；
(3) presoma obtained by step (2) is subjected to high-temperature calcination, chitin or chitin derivativ carbon under an inert atmosphere
Evaporation characteristic is melted using inorganic salts during change, porous hard carbon material is made in situ.
Under concrete condition, the present invention, as carbon source, is that reserves are the most in nature using chitin or chitin derivativ
One of natural polymer abundant, has cheap, easily obtains and the advantages such as recyclable.Inventor also found that the material has
Naturally abundant nitrogen source, abundant nitrogen can guarantee the high electronic conductance of material, mention for high capacity, the high rate charge-discharge of battery
Basis is supplied.
Under preferable case, using chitin derivativ chitosan as carbon source, chitosan is that chitin is de- through concentrated base processing
It goes obtained from acetyl group therein, the chitin after removing acetyl group reforms into soluble chitosan,To be very suitable to
It is uniformly mixed in the inorganic salt solution in the present invention.In more preferable situation, the viscosity of chitosan is selected in 100-
200mpa.s。
Under preferable case, in step (1), inorganic salts are selected from NaCl, KCl, CaCl2、MgCl2, the additional amounts of inorganic salts with
It is 1:2-1:0.5 that chitin or chitin derivativ, which are according to mass ratio,.In more preferable situation, inorganic salts select NaCl.
Under preferable case, in step (1), cosolvent is selected from H2CO3、CH3The mass concentration of COOH, HClO, cosolvent is
0.1%-10%.In more preferable situation, cosolvent selects CH3COOH。
Under preferable case, in step (2), with refrigerator freezing or liquid nitrogen flash freezer, be dried in vacuo vacuum degree 10-20Pa it
Between, between drying time 60-72h.
Under preferable case, in step (3), inert atmosphere is nitrogen or argon gas or both mixed gas, and calcination temperature is
Between 1200-1400 DEG C, calcination time is between 2-4h.
Second aspect of the present invention provides a kind of negative electrode material, wherein the negative electrode material uses first aspect present invention institute
The method preparation stated, microscopic appearance are three-dimensional cross-linked reticular structure, and pore diameter range more extensively shows as 1-200nm, whole to tie
Structure is having a size of 50-100 μm.
The third aspect of the present invention provides a kind of sodium-ion battery, is coated with this hair on the collector of the sodium-ion battery
Negative electrode material described in bright second aspect.The negative electrode material by after being mixed with conductive black, binder formed electrode slurry into
Row coating is finally assembled into together with diaphragm, electrolyte and anode containing sodium-ion battery of the invention.
Compared with prior art, product of the invention and method at least have the advantage that
(1) negative electrode material of the invention has three-dimensional crosslinked network form, and specific surface is big, mutually interconnects between inside configuration hole
It connects, not only facilitates and reduce electrode in the polarization phenomena in electrochemical process and increase contact between electrode and electrolyte,
It is more advantageous to quick diffusion of the sodium ion in electrode material；
(2) negative electrode material of the invention shows the property by nanoaperture, and sodium ion is embedding in nano material
It is short to enter depth as shallow, diffusion path, is conducive to sodium ion quick deintercalation in the material；
(3) preparation method of the present invention is extremely simple, at low cost, sufficiently melts and evaporates using the salt in our lives
Characteristic, in-situ construction porous material；
(4) negative electrode material prepared by the present invention can be realized reversible charge and discharge, good cycle, and capacity is reported at this stage
In there is leading superiority, high rate performance is prominent, and high rate during charging-discharging is stablized.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that embodiment 1 is prepared.
Fig. 2 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that embodiment 2 is prepared.
Fig. 3 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that embodiment 3 is prepared.
Fig. 4 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that embodiment 4 is prepared.
Fig. 5 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 1 is prepared.
Fig. 6 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 2 is prepared.
Fig. 7 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 3 is prepared.
Fig. 8 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 4 is prepared.
Fig. 9 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 5 is prepared.
Figure 10 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 6 is prepared.
Figure 11 is the scanning electron microscope (SEM) photograph for the negative electrode material powder that comparative example 7 is prepared.
Figure 12 is voltage and 1A g of the battery that is prepared of test example 3 in 0.01-3.0V-1Current density under recycle
300 cycle performance figures.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The method that negative electrode material is prepared in situ in inorganic salts melting evaporation of the invention, comprising the following steps:
(1) dissolve sodium chloride in deionized water, and chitosan be added in the solution, be added dropwise glacial acetic acid to completely it is molten
Solution, transparent glue.
In the present invention, the chitosan is selected as viscosity in 100-200mpa.s.
In the present invention, mass concentration of the glacial acetic acid solvent in the system is 0.1%-10%.
It is 1:2-1:0.5 that concentration of the sodium chloride in the system, which is according to mass ratio with chitosan,.
Wherein the order of addition of four kinds of substances has a major impact system.
Preferably, NaCl is add to deionized water stirring to being completely dissolved first, then adds Chitosan powder, to molten
Glacial acetic acid solution is added dropwise in liquid after mixing, and continues to stir.
The mode of the stirring is strength magnetic agitation, and the speed of the stirring is 200-500rpm.
Preferably, the time of the stirring is 12-24 hour.
(2) colloid transparent obtained by step (1) is removed under condition of high vacuum degree and ultralow temperature wherein moisture, is placed in pipe
In formula furnace under atmosphere of inert gases 1200-1400 DEG C high-temperature calcination 2-4 hours.
In the present invention, the temperature of the high vacuum ultralow temperature is -80~-100 DEG C, and vacuum degree maintains
10-20Pa.In the present invention, the heating rate is 2-5 DEG C/min.
(3) grinding char-forming material obtained by (2) can be used as electrode material at 50 μm or so particles.
Prepared by the method negative electrode material can be used to prepare electrode slurry, wherein contain this hair in electrode slurry
Bright negative electrode material.Electrode slurry is coated on battery afflux liquid, the battery containing negative electrode material of the invention is assembled into.
In the present invention, the composition of the electrode slurry is referred to the mode of this field routine, for example, the electrode slurry
Material may include: negative electrode material of the invention, conductive black and binder.The electrode slurry can be by mixing mentioned component
Conjunction obtains.
In the present invention, on the basis of the weight of the electrode slurry, the content of the negative electrode material can be 70-90 weight
% is measured, the content of the conductive black can be 5-15 weight %, and the content of the binder can be 5-15 weight %；It is preferred that
Ground, on the basis of the weight of the electrode slurry, the content of the negative electrode material can be 75-85 weight %, the conduction charcoal
Black content can be 7-13 weight %, and the content of the binder can be 7-13 weight %.
In the present invention, the conductive black and the binder all can be this field it is conventional for making battery electricity
The conductive black and binder of pole slurry.Wherein the binder for example can be the Kynoar of 5 weight %.
In the present invention, there is no particular limitation for the diaphragm of the sodium-ion battery, can for this field routine sodium from
The diaphragm of sub- battery, for example, trade mark are the diaphragm of Whatman GF/C.
In the present invention, the electrolyte can be the electrolyte of this field routine, for example, NaPF6, ethylene carbonate
(EC) and the mixed liquor of diethyl carbonate (DEC), wherein the volume ratio of EC:DEC can be 1:0.9-1.1, NaPF6Concentration can
Think 0.8-1.1mol/L.
Sodium-ion battery of the invention being capable of specific discharge capacity and capacity retention ratio with higher.
The present invention will be described in detail by way of examples below.In the following Examples and Comparative Examples, using model
Scanning electron microscope for QUANTA FEG250 (purchased from section depending on reaching (China) Co., Ltd) is scanned Electronic Speculum observation.
Embodiment 1-4 and comparative example 1-7 is for illustrating negative electrode material of the invention.
Embodiment 1
(1) according to the quality of substance than chitosan: sodium chloride=1:1 weighs 2g chitosan and 2g sodium chloride respectively.
(2) 80mL deionized water is added in beaker, the sodium chloride weighed up is added and is stirred at room temperature to being completely dissolved.
(3) Chitosan powder is added in sodium chloride solution, is sufficiently stirred, measurement 1mL glacial acetic acid is added dropwise to molten
In liquid, the very sticky of change is reinforced magnetic agitation by solution during being somebody's turn to do.To solution be translucent shape continue stirring 12 hours.
(4) colloid obtained in (3) is transferred to freezing environment 12 hours, is then carried out before vacuum drying obtains for 72 hours
Drive body.
(5) substance is placed in porcelain boat, 1200 DEG C is heated under argon atmosphere, heat preservation obtains char-forming material in 2 hours.
(6) char-forming material that (5) obtain is placed in mortar and is ground sufficiently, be labeled as S1.
The negative electrode material powder that embodiment 1 is prepared is observed under scanning electron microscope, scanning electron microscope (SEM) photograph (SEM figure) is shown in figure
1。
Embodiment 2
(1) carry out according to the method for embodiment 1, wherein except that heat treatment time be 4 hours, 1200 DEG C of temperature,
Corresponding cathode dusty material is obtained, S2 is labeled as.
Electron microscope analysis is scanned to embodiment 2 and sees Fig. 2, wherein sodium chloride prepares material structure under this condition and implements
Example 1 is similar, all has porous network shape structure.
Embodiment 3
(1) it carries out according to the method for embodiment 1, wherein the time is to protect except that the temperature of heat treatment is 1400 DEG C
Temperature 2 hours.Corresponding cathode dusty material is obtained, S3 is labeled as.
The negative electrode material powder that embodiment 3 obtains is observed under a scanning electron microscope, scanning electron microscope (SEM) photograph such as Fig. 3 institute
Show.
Embodiment 4
(1) it carries out according to the method for embodiment 1, wherein the time is to protect except that the temperature of heat treatment is 1400 DEG C
Temperature 4 hours.Corresponding cathode dusty material is obtained, S4 is labeled as.
The negative electrode material powder that embodiment 4 obtains is observed under a scanning electron microscope, scanning electron microscope (SEM) photograph such as Fig. 4 institute
Show.
By Fig. 1-4 it can be observed that under the conditions of above-described embodiment, melting evaporation process, and shell completely occurs for sodium chloride
Chitosan material is adequately carbonized, to create abundant and three-dimensional cross-linked porous network structure is presented.
Comparative example 1
(1) according to the quality of substance, 2g chitosan is weighed.
(2) 80mL deionized water is added in beaker.
(3) Chitosan powder is added in deionized water solution, is sufficiently stirred, measured 1mL glacial acetic acid and be added dropwise to
In solution, the very sticky of change is reinforced magnetic agitation by solution during being somebody's turn to do.It is small to continue stirring 12 to the transparent glue of solution
When.
(4) solution obtained in (3) is transferred to freezing environment 12 hours, is then carried out before vacuum drying obtains for 72 hours
Drive body.
(5) substance is placed in porcelain boat, 800 DEG C is heated under argon atmosphere, heat preservation obtains char-forming material in 2 hours, marks
It is denoted as D1.
The negative electrode material powder that comparative example 1 is prepared is observed under scanning electron microscope, scanning electron microscope (SEM) photograph (SEM figure) is shown in figure
5.From figure 5 it can be seen that the negative electrode material that comparative example 1 is prepared is in solid micron laminated structure, the thickness of the piece is in 10-
20 μm, surface is smooth to there is not hole configurations.
Comparative example 2
It is carried out according to the method for comparative example 1, wherein heat preservation 2 hours obtains except that heat treatment temperature is 1000 DEG C
Corresponding cathode dusty material is labeled as D2.
The raising of analysis our predicted temperatures of comparative example 1 and comparative example 2 is beneficial to the increase of the material degree of order.Comparative example
2 scanning electron microscope (SEM) photograph is shown in Fig. 6.
Comparative example 3
According to comparative example 1 method carry out, wherein except that heat treatment temperature be 1200 DEG C, keep the temperature 2 hours.
To corresponding cathode dusty material, it is labeled as D3.
Comparative example 3 is consistent with comparative example 1 and 2 rule of comparative example, and material interlamellar spacing is gradually increased with temperature raising.It will be right
The negative electrode material powder that ratio 3 obtains is observed under a scanning electron microscope, and scanning electron microscope (SEM) photograph is as shown in Figure 7.
Comparative example 4
It is carried out according to the method for comparative example 1, the difference is that heat treatment temperature is 1400 DEG C, keeps the temperature 2 hours.Final
To negative electrode material powder, it is denoted as D4.
Interlamellar spacing in comparison D1/D2/D3 material gradually increases.Therefore temperature plays degree of graphitization and interlamellar spacing
Very big influence.
The negative electrode material powder that comparative example 4 is prepared is observed under scanning electron microscope, scanning electron microscope (SEM) photograph (SEM figure) is shown in figure
8。
From in Fig. 5-8, as can be seen that treated at a temperature of this four kinds, material overall structure is similar, shows as thick piece
Shape composition.Body structure surface and inside do not have porose appearance in the case where no sodium chloride.
Comparative example 5
It carries out according to the method for embodiment 1, wherein the time is heat preservation except that the temperature of heat treatment is 1400 DEG C
0.5 hour.Corresponding cathode dusty material is obtained, D5 is labeled as.
The negative electrode material powder that comparative example 5 obtains is observed under a scanning electron microscope, scanning electron microscope (SEM) photograph such as Fig. 9 institute
Show.
Comparative example 6
It carries out according to the method for embodiment 1, wherein the time is heat preservation 1 except that the temperature of heat treatment is 1400 DEG C
Hour.Corresponding cathode dusty material is obtained, D6 is labeled as.
The negative electrode material powder that comparative example 6 obtains is observed under a scanning electron microscope, scanning electron microscope (SEM) photograph such as Figure 10 institute
Show.
Comparative example 7
(1) according to the quality of substance than chitosan: potassium hydroxide=1:1 weighs 2g chitosan and potassium hydroxide respectively.
(2) 80mL deionized water is added in beaker, Chitosan powder is added in deionized water, is sufficiently stirred, measures
1mL glacial acetic acid is added dropwise in solution, and the very sticky of change is reinforced magnetic agitation by solution during being somebody's turn to do.To colloid in saturating
Bright shape continues stirring 12 hours.
(3) potassium hydroxide weighed up is added in (2) to be stirred at room temperature uniformly.
(4) solution obtained in (3) is transferred to freezing environment 12 hours, is then carried out before vacuum drying obtains for 72 hours
Drive body.
(5) substance is placed in porcelain boat, 1400 DEG C is heated under argon atmosphere, heat preservation obtains char-forming material in 2 hours.
(6) char-forming material that (5) obtain is placed in a beaker and is separately added into hydrochloric acid and deionized water is sufficiently stirred and surpasses
Sound obtains material by high speed centrifugation method.Then it carries out oven drying and obtains material requested, be labeled as D7.
The negative electrode material powder that comparative example 7 is prepared is observed under scanning electron microscope, scanning electron microscope (SEM) photograph (SEM figure) is shown in figure
11.It can be seen from fig. 11 that passing through in the method obtained electrode material of conventional alkalization pore-creating, the hole and Ben Fa of formation
The mechanism of fuse salt pore-creating in bright is significantly different.The hole for the material being prepared by a conventional method show as occur chemical reaction and
Corrode hole out, the surface and inside of material entirety do not change significantly.However pore-creating is being carried out using sodium chloride
When, the structure of material entirety has occurred obvious and uniformly changes, and the internal structure of material and the outside of material are all presented
A kind of three-dimensional crosslinked network shape is gone out.Therefore will have more from the negative electrode material that material processing mode melting salt treatment obtains
Big specific surface and preferable Ionic diffusion energy.
Test example 1
(1) by the resulting negative electrode material S1 of embodiment 1 and conductive black (trade mark SP, producer TIMCAL, the same below), bonding
Agent is that (mixed solution of 5 weight %, trade mark U.S. Su Wei 1015, producer's Dongguan City gold ship plastic cement original to Kynoar PVDF
Material company, the same below) mixed according to weight ratio 8:1:1, obtain electrode slurry；
(2) negative electrode tab is made in step (1) the electrode obtained slurry smear on copper foil, using sodium piece as cathode, Whatman
GF/C (Whatman company, producer) is diaphragm, electrolyte NaPF6+ ethylene carbonate (EC)+diethyl carbonate (DEC) is mixed
Closing liquid, (wherein the volume ratio of EC:DEC is 1:1, NaPF6Concentration be 1mol/L), full of argon atmosphere glove box in group
Dress up model CR2025 experiment button cell.
Test example 2-4
According to the method assembled battery of test example 1, the difference is that using the resulting negative electrode material of embodiment 2-4 respectively
S2-S4。
Comparative experimental example 1-7
According to the method assembled battery of test example 1, the difference is that using the resulting negative electrode material of comparative example 1-7 respectively
D1-D7。
Test case
(1) after standing 12h to sodium-ion battery obtained by test example 1-4 and comparative example test example 1-7 respectively, in LAND CT-
Charge and discharge cycles 50 times tests are carried out on 2001A tester (Wuhan Land Electronic Co., Ltd.), specifically: in 0.01-
The voltage and 20mA g of 3.0V-1Current density under, by battery charging and discharging recycle 50 times；Detect initial charge specific capacity (mAh
g-1) and charge and discharge cycles 50 times after charge specific capacity (mAh g-1), and calculate charge and discharge cycles 50 times capacity retention ratio (=
Charge specific capacity ÷ initial charge specific capacity × 100% after charge and discharge cycles 30 times), result is remembered in table 1.
(2) by taking test example 3 as an example, by the sodium-ion battery being prepared 0.01-3.0V voltage and 1A g-1Electric current
300 cycle performances are recycled under density and are recorded in Figure 12, it can be recognized from fig. 12 that in the voltage and 1A g of 0.01-3.0V-1's
Under current density, the charging and discharging capacity of battery be can still be maintained in very high very stable state, and capacity retention ratio reaches
85%.
Table 1
As it can be seen from table 1 the initial charge specific capacity of the resulting sodium-ion battery of test example 3 according to the present invention, 50
Specific discharge capacity and capacity retention ratio are intended to be significantly higher than comparative example after secondary circulation.
By comparative experimental example 1, test example 2, test example 3 and test example 4 as can be seen that being handled in optimal conditions
To material show more excellent chemical property.
By the way that comparative experimental example 1, comparative experimental example 2, comparative experimental example 3 and comparative experimental example 4 can be seen that difference
Temperature Treatment chitosan material, it is closely similar on pattern, it is microcosmic upper to show the smooth solid laminated structure in surface.But from
From the point of view of in electrochemical data as the temperature rises, charge specific capacity gradually rises in charge and discharge process.Therefore with temperature
The degree of order of material will be promoted constantly while raising, and the defect of material internal gradually decreases.Therefore in subsequent processing
It chooses 1400 DEG C and is modified processing.
By test example 3, comparative experimental example 5 and comparative experimental example 6 being compared as can be seen that soaking time is by 2
During a hour is gradually reduced to 1 hour, material internal hole is gradually decreased, and aperture becomes larger and irregularly.Cause
This specific surface of comparative example 5 and comparative example 6 in electrochemical reaction process is smaller, the penetrability in internal aperture
Difference, thus it is unfavorable to the diffusion of ion.
By the way that test example 3 and comparative experimental example 7 compare as can be seen that when selecting different salt to be handled, material
Material shows the mode in entirely different hole.The uniform pore diameter handled by simple sodium chloride, large specific surface area, internal holes
Three-dimensional connection type is presented in gap.And the hole of the material obtained by traditional potassium hydroxide treatment shows as leaving a trace after etching
The form in hole.Perforative network structure is not formed around hole, it is whole still to show as solid block structure, therefore
The specific surface of the structure is smaller, is unfavorable for the infiltration of electrolyte, and active site is few.Compared to easy sodium chloride processing mode,
This method does not have strong corrosivity not only and is unfavorable for material storage sodium.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.In addition, a variety of different implementations of the invention
Any combination can also be carried out between mode, as long as it does not violate the idea of the present invention, it is public equally to should be considered as institute of the invention
The content opened.
Claims (7)
1. a kind of method that porous hard carbon cathode material is prepared in situ in inorganic salts melting evaporation, which is characterized in that the method packet
Include following steps:
(1) inorganic salt solution is prepared first, and chitin or chitin derivativ powder is then added, is slowly added to cosolvent,
Lasting stirring or ultrasound obtain uniform colloidal sol；
(2) colloidal sol obtained by step (1) is freezed and is dried in vacuo to obtain fluffy presoma；
(3) presoma obtained by step (2) is subjected to high-temperature calcination under an inert atmosphere, what chitin or chitin derivativ were carbonized
Evaporation characteristic is melted using inorganic salts in the process, porous hard carbon material is made in situ.
2. according to the method described in claim 1, wherein, in step (1), inorganic salts are selected from NaCl, KCl, CaCl2、MgCl2,
It is 1:2-1:0.5 that the additional amount of inorganic salts, which is according to mass ratio with chitin or chitin derivativ,.
3. according to the method described in claim 1, wherein, in step (1), cosolvent is selected from H2CO3、CH3COOH, HClO are helped
The mass concentration of solvent is 0.1%-10%.
4. according to the method described in claim 1, wherein, in step (2), with refrigerator freezing or liquid nitrogen flash freezer, being dried in vacuo
Between vacuum degree 10-20Pa, between drying time 60-72h.
5. according to the method described in claim 1, wherein, in step (3), inert atmosphere is nitrogen or argon gas or both mixing
Gas, calcination temperature are between 1200-1400 DEG C, and calcination time is between 2-4h.
6. a kind of negative electrode material, which is characterized in that the preparation of the method as described in any one of claim 1-5, microcosmic shape
Looks are three-dimensional cross-linked reticular structure.
7. a kind of sodium-ion battery, which is characterized in that be coated on the collector of the sodium-ion battery as claimed in claim 6 negative
Pole material.
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