CN109592677A - A kind of expansion interlamellar spacing microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery - Google Patents
A kind of expansion interlamellar spacing microcrystalline graphite material and preparation method thereof and the application in sodium-ion battery Download PDFInfo
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- CN109592677A CN109592677A CN201811476835.9A CN201811476835A CN109592677A CN 109592677 A CN109592677 A CN 109592677A CN 201811476835 A CN201811476835 A CN 201811476835A CN 109592677 A CN109592677 A CN 109592677A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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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
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Application the invention discloses a kind of expansion interlamellar spacing microcrystalline graphite material and preparation method thereof and in sodium-ion battery, expanding interlamellar spacing microcrystalline graphite material preparation process is that micro crystal graphite micro mist is obtained purifying micro crystal graphite by acid solution purification processes；The purifying micro crystal graphite carries out oxidation intercalation processing, obtains oxidation micro crystal graphite；The oxidation micro crystal graphite is 10~100m to get specific surface area by reduction treatment2/g；Interlamellar spacing is the expansion interlamellar spacing microcrystalline graphite material of 0.373~0.394nm；This method raw material is easy to get, and preparation process is simple, reproducible；Preparation, which expands interlamellar spacing micro crystal graphite, has the characteristics that big interlamellar spacing, surface functional group abundant, moderate specific surface area, excellent electric conductivity and good mechanical strength, cathode as sodium ion secondary battery, coulombic efficiency, excellent high rate performance and long circulating stability energy with higher, while there is high tap density and low cost.
Description
Technical field
The present invention relates to a kind of modification of microcrystalline graphite material, in particular to a kind of expansion interlamellar spacing microcrystalline graphite material, also
It is related to expanding the method for interlamellar spacing microcrystalline graphite material by oxidation intercalation and reduction preparation, further relates to expand interlamellar spacing microlite
Application of the ink as Carbon negative electrode material of sodium ion battery, belongs to secondary cell field.
Background technique
Graphite is a kind of carbon material for possessing good layer structure, and the material high temperature resistant is corrosion-resistant, has good conduction
Property, thermal conductivity and stable chemical property.Graphite has electronic conductivity height, layer structure volume change before and after embedding lithium simultaneously
The high advantages such as low with intercalation potential of small, embedding lithium capacity, yield unusually brilliant results in the energy storage field being concerned, it has also become mainstream at present
Commercial Li-ion battery negative electrode material.However, since lithium resource reserves are less, the reasons such as the recycling of lithium and extraction difficulty are led
Cause lithium ion battery cost high, the further application of lithium ion battery and graphite material is restricted.
Sodium-ion battery relies on the rich reserves of sodium, becomes the research hotspot of secondary cell system of new generation.However it compares
In lithium ion battery, sodium-ion battery has the problems such as cathode voltage height and big sodium ion radius, to efficient sodium-ion battery
Exploitation proposes many problems.Although the reaction mechanism of sodium-ion battery is identical as lithium ion battery, however sodium ion radius ratio
Lithium ion is big by 55%, and insertion and diffusion of the sodium ion in mutually isostructural graphite are often extremely difficult, while the stone after insertion
Ink structure variation can it is bigger, therefore the specific capacity of electrode and chemical property all can phase strain differential, therefore common graphite be not suitable for
Negative electrode material as sodium-ion battery.Sodium-ion battery field, which generally believes, possesses bigger interlamellar spacing, more micro-nano hole knots
The hard carbon material of structure is the ideal chose of anode material of lithium-ion battery, however hard carbon material poorly conductive, and preparation cost
Height limits the high rate performance and price advantage of sodium-ion battery.Recently, it is believed that expand interlamellar spacing graphite material have it is uncommon
It hopes and plays storage sodium performance, sight is then thrown back graphite material again.
Natural graphite has crystalloid (flakey) graphite and crystallite (earthy) graphite.Scaly graphite scale is big, aggregate orientation
Property is good.Micro crystal graphite crystal diameter is usually less than 1 μm, is in crystallite aggregate, is in Turbostratic, therefore is industrially not so good as scale stone
Ink is widely used, but its price is lower, and average interlamellar spacing is bigger, and Turbostratic is easier to further prepare the stone for expanding interlamellar spacing
Ink material.The research for preparing expanded graphite by micro crystal graphite is more rare, this is because micro crystal graphite and common expanded graphite
Raw material Scaly graphite compares, and the two has notable difference in terms of chemically reacting attribute, crystalline orientation.Thus, it adopts
It is never had to capture with traditional handicraft and prepares the technical method for expanding the micro crystal graphite of interlamellar spacing using micro crystal graphite.
Traditional method for preparing expanded graphite includes chemical graft process and high-temperature expansion method, but due to micro crystal graphite and
Difference in crystalline flake graphite structure leads to the effect for preparing expansion micro crystal graphite in this way and bad, carbon-coating spacing expansion
Degree it is little, and the entrance during intercalation containing element sulphur during further heat treatment into air so that release
The pernicious gases such as a large amount of sulfur dioxide, cause environmental pollution.In addition the gas moth overflowed when high-temperature process has lost material itself,
A large amount of macropores are left, the coulombic efficiency of material is reduced.
Therefore, the graphite material for expanding interlamellar spacing how is prepared, and avoids the above problem, at long-standing problem scientific research work
The problem of author.
Summary of the invention
Existing micro crystal graphite for secondary battery cathode material there are aiming at the problem that, the purpose of the invention is to provide
A kind of interlamellar spacing is big, specific surface area is suitable, good conductivity and superior electrical conductivity and expansion interlamellar spacing the features such as mechanical strength
Microcrystalline graphite material.
Another object of the present invention be to provide a kind of simple process, it is reproducible, low in cost, environmental-friendly,
Be suitble to large-scale production prepares a kind of above-mentioned method for expanding interlamellar spacing microcrystalline graphite material.
The third object of the present invention is to provide the application for being made and expanding interlamellar spacing microcrystalline graphite material, be used for sodium from
Sub- battery, it is intended to which the electric property for promoting sodium-ion battery obtained such as improves its specific capacity and long-term cycle stability energy.
It in order to achieve the above technical purposes, should the present invention provides a kind of preparation method for expanding interlamellar spacing micro crystal graphite
Method the following steps are included:
1) micro crystal graphite micro mist is obtained into purifying micro crystal graphite by acid solution purification processes；
2) the purifying micro crystal graphite carries out oxidation intercalation processing, obtains oxidation micro crystal graphite；
3) the oxidation micro crystal graphite by reduction treatment to get.
Preferred scheme, the acid solution is by concentrated hydrochloric acid and dense hydrofluoric acid and water 0.8~1.5:1:0.5~1.5 by volume
Composition.The removal effect of ash content in natural micro crystal graphite can be improved, with respect to single acid using mixed acid to obtain high-purity
Micro crystal graphite, purity can achieve 99% or more.The volume ratio of more preferably scheme, concentrated hydrochloric acid and dense hydrofluoric acid and water be 1~
1.2:1:0.5~1.Concentrated hydrochloric acid and dense hydrofluoric acid are the technical grade acid that can directly buy on the market.
Preferred scheme, the acid solution purification processes process are as follows: micro crystal graphite micro mist is placed in acid solution, 60~100
At a temperature of DEG C, handle 10~36 hours.Preferred scheme can obtain the micro crystal graphite that purity is higher than 99%.More preferably side
Case, the temperature of nitration mixture processing are 80~90 DEG C, and the time of nitration mixture processing is 18~24 hours.
Preferred scheme, the oxidation intercalation process are as follows: by purifying micro crystal graphite and sodium nitrate, the concentrated sulfuric acid and Gao Meng
Sour potassium mixing, is placed in 30~40min of stirring in ice-water bath, adds hydrogen peroxide solution and continue 5~15min of stirring, aoxidized
Micro crystal graphite；
The matter of preferred scheme, the micro crystal graphite and sodium nitrate, the concentrated sulfuric acid, potassium permanganate and 60wt% hydrogen peroxide solution
Amount is than being 20~40:3~6:100~180:10~30:60~100；More preferably mass ratio are as follows: 20~40:3~6:120~
160:20~25:70~80.
Preferred scheme, the reduction treatment process are as follows: mix oxidation micro crystal graphite with reducing solution, 40~60
At a temperature of DEG C, 12~36h is stirred to get interlamellar spacing micro crystal graphite is expanded.
Preferred scheme, the reducing solution include hydrazine hydrate solution, ascorbic acid solution, sodium sulfite solution, Asia
At least one of ferrous sulfate, hydroiodic acid solution.It is more preferably hydrazine hydrate solution, sodium sulfite solution or hydroiodic acid solution.
Preferred scheme, the reducing solution concentration are 0.3~5mol/L.
The ratio of preferred scheme, the reducing solution and oxidation micro crystal graphite is 3~10mL/g.More preferably ratio
For 5~8mL/g.
The present invention also provides a kind of expansion interlamellar spacing micro crystal graphites, are prepared by the above method.
Preferred scheme, the specific surface area for expanding interlamellar spacing micro crystal graphite is 10~100m2/ g, interlamellar spacing be 0.373~
0.394nm.Expansion interlamellar spacing micro crystal graphite of the invention possesses suitable specific surface area and interlamellar spacing and surface function abundant
Group.More preferably scheme, the specific surface area for expanding interlamellar spacing micro crystal graphite is 40~60m2/ g, interlamellar spacing be 0.380~
0.390nm。
Expansion interlamellar spacing microcrystalline graphite material of the invention is improved primarily directed to carbon material in the prior art.Especially
Although its be as anode material of lithium-ion battery in use, existing hard carbon material storage sodium ability it is strong, its material is intrinsic
Poorly conductive, it is poor with negative electrode material high rate performance made of it, and also its manufacturing cost is high；And existing graphite material average layer
Spacing is small, is not suitable for sodium ion in storage wherein.Technical solution of the present invention devises a kind of expansion interlamellar spacing micro crystal graphite material
Material possesses the interlamellar spacing and surface bigger compared to general graphite with functional group abundant, effectively increases the storage of material
Sodium capacity, and the intrinsic conductivity for expanding interlamellar spacing microcrystalline graphite material is excellent, is conducive to the raising of battery high rate performance；Relatively
The volume enlargement layer pitch problems during sodium ion is embedded in and deviates from the material have been effectively relieved in bigger interlamellar spacing, improve
The cyclical stability of material.
Expansion interlamellar spacing microcrystalline graphite material of the invention uses low-cost micro crystal graphite for raw material, advantageously reduces
Material cost.
The present invention also provides the applications for expanding interlamellar spacing microcrystalline graphite material, answer as anode material of lithium-ion battery
With.
The preparation method provided by the invention for expanding interlamellar spacing micro crystal graphite, comprising the following specific steps
Step (1): micro crystal graphite is added to crusher and cut broken, 200 mesh mesh screens is then crossed and sieve
To micro crystal graphite micro mist, then by ultrasonic nitration mixture purification removal ash content, the microlite ink powder purified；
Step (2): obtained micro crystal graphite in (1) is mixed with sodium nitrate, the concentrated sulfuric acid, potassium permanganate, in ice-water bath
30~40min is stirred, 60wt% hydrogen peroxide is then added and continues to stir 10min, then filters, obtained bright yellow solid is repeatedly
Washing obtains oxidation micro crystal graphite；
Step (3): oxidation micro crystal graphite obtained in (2) is mixed with reducing solution, the magnetic agitation at 50 DEG C
For 24 hours, it filters, the solid that deionized water is washed repeatedly, obtains expanding interlamellar spacing micro crystal graphite.
The present invention, by the oxidation intercalation of acid group molecule, expands carbon-coating during preparation expands interlamellar spacing micro crystal graphite
Spacing, then expand interlamellar spacing graphite by the way that reducing solution stirring reduction preparation is added.It is prepared with this technical solution and expands interlayer
During away from micro crystal graphite, the pernicious gases such as sulfur dioxide will not be discharged into air.
More preferably scheme, the reducing solution are as follows: hydrazine hydrate solution, sodium sulfite solution or hydroiodic acid solution are wherein
One kind.
Expansion interlamellar spacing microcrystalline graphite material stable structure of the invention, ability of anti-deformation is good, has good sodium ion
It is embedded in abjection ability.The material also has good electric conductivity, and moderate specific surface area is shown as sodium-ion battery cathode
High specific capacity, good high rate performance and long circulating stability energy.
Expansion interlamellar spacing microcrystalline graphite material of the invention can be used existing for the preparation method of sodium-ion battery cathode
Method passes through rubbing method for example, the expansion interlamellar spacing microcrystalline graphite material that the present invention obtains is mixed with conductive agent and binder
Coated in copper foil current collector, sodium-ion battery cathode is made.
It is prepared by the present invention expand interlamellar spacing microcrystalline graphite material as negative electrode material prepare sodium-ion battery method and
Method for testing performance: weighing above-mentioned expansion interlamellar spacing microcrystalline graphite material, 10wt.%Super P is added as conductive agent,
10wt.% sodium carboxymethylcellulose (CMC) is used as binder, it is ground sufficiently after a small amount of deionized water be added be mixed to form
These slurries are coated in copper foil current collector as test electrode, as a comparison with metallic sodium piece by even black paste slurry
Electrode assembling becomes button cell, uses electrolyte system for 1M NaClO4/EC:DEC(1:1).Used in test loop performance
Charging and discharging currents density is 100mA/g.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1) the expansions interlamellar spacing microcrystalline graphite material of technical solution of the present invention preparation has big carbon-coating spacing and properly
Specific surface area, bigger carbon-coating spacing (> 0.37nm) provides space for the storage of sodium ion, improves the storage sodium ratio of material
Capacity, bigger carbon-coating spacing is smaller in migration resistance wherein for sodium ion, advantageous to the transmission dynamics of sodium ion, together
When big interlamellar spacing sodium ion has been effectively relieved during embedding de- caused by volume expand interlamellar spacing, improve the circulation of material
Service life；Material surface has a considerable number of functional group, this improves the fake capacitance characteristic of material, furthermore material intrinsic conductivity
Good, these all improve the high rate performance of material.
2) the method operation that preparation expands interlamellar spacing microcrystalline graphite material in the present invention eliminates the expansion of traditional handicraft high temperature
Big interlamellar spacing treatment process with replaced safer Liquid reduction reaction process, and avoids the row of the pernicious gases such as sulfur dioxide
It puts, avoids the reduction for causing macropore to be formed by gas overflowing and causing coulombic efficiency.Operation of the present invention method is simple and reliable, again
Renaturation is good, strong operability, environmental-friendly, low in cost, is suitable for large-scale production.
3) expansion interlamellar spacing microcrystalline graphite material of the invention is as sodium ion secondary battery negative electrode material application, preparation
Sodium-ion battery is with higher to have high coulombic efficiency, excellent high rate performance and long circulating stability energy, while having height
Tap density and lower cost.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture for expanding interlamellar spacing micro crystal graphite.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
It takes 20g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With technical-grade hydrochloric acid: industrial stage hydrofluoric acid: deionized water volume ratio is that 5:3:2 is made into 100ml mixed acid solution, will
Microlite ink powder pours into the mixed acid solution, carries out heating stirring with magnetic stirring apparatus, whipping temp is 80 DEG C, nitration mixture processing
Time is 12h；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in
Ash impurities in micropore, sonic oscillation time are 20min；Then it uses deionized water filtration washing 3 times again；It is put into baking oven
60 DEG C of heat preservation 6h, the microlite ink powder purified；By obtained micro crystal graphite and 6g sodium nitrate, 160g (100mL) concentrated sulfuric acid,
25g potassium permanganate mixes, and stirs 30min in ice-water bath, and it is that 60% hydrogen peroxide solution continues to stir that 80g content, which is then added,
10min is then filtered, and obtained bright yellow solid washs repeatedly, obtains oxidation micro crystal graphite；The oxidation micro crystal graphite that will be obtained
It is mixed with the hydrazine hydrate solution that 150mL concentration is 3mol/L, magnetic agitation for 24 hours, wash repeatedly by filtering, deionized water at 50 DEG C
Obtained solid obtains expanding interlamellar spacing micro crystal graphite, the expansion interlamellar spacing microcrystalline graphite material specific surface of embodiment preparation
Product is 12.5m2/g；The expansion interlamellar spacing micro crystal graphite interlamellar spacing is 0.390nm.It is made and expands interlamellar spacing micro crystal graphite
Transmission electron microscope picture (TEM) is shown in Fig. 1.
80wt.% expansion interlamellar spacing microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added and makees
For conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionized water is sufficiently added later
It is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metallic sodium
Electrode assembling becomes button cell to piece as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1),
Under the current density of 50mA/g, test loop performance；Battery is tested under the different current density such as 1000mA/g, 2000mA/g
High rate performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property: in 50mA/g
Current density under, first circle coulombic efficiency be 71%, first circle discharge capacity be 366mA/g, circulation 100 circle after, be still able to maintain
The specific capacity of 291mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 241mAh/g and
The specific capacity of 201mAh/g.
Embodiment 2
It takes 20g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With technical-grade hydrochloric acid: industrial stage hydrofluoric acid: deionized water volume ratio is that 5:3:2 is made into 100ml mixed acid solution, will
Microlite ink powder pours into the mixed acid solution, carries out heating stirring with magnetic stirring apparatus, whipping temp is 70 DEG C, nitration mixture processing
Time is 18h；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in
Ash impurities in micropore, sonic oscillation time are 20min；Then it uses deionized water filtration washing 3 times again；It is put into baking oven
60 DEG C of heat preservation 6h, the microlite ink powder purified；By obtained micro crystal graphite and 5g sodium nitrate, 140g (87.5mL) dense sulphur
Acid, 20g potassium permanganate mix, and stir 30min in ice-water bath, and it is that 60% hydrogen peroxide solution continues to stir that 70g content, which is then added,
10min is then filtered, and obtained bright yellow solid washs repeatedly, obtains oxidation micro crystal graphite；The oxidation micro crystal graphite that will be obtained
It is mixed with the hydroiodic acid solution that 100mL concentration is 2mol/L, magnetic agitation for 24 hours, wash repeatedly by filtering, deionized water at 50 DEG C
Obtained solid obtains expanding interlamellar spacing micro crystal graphite, the expansion interlamellar spacing microcrystalline graphite material specific surface of embodiment preparation
Product is 22.8m2/g；The expansion interlamellar spacing micro crystal graphite interlamellar spacing is 0.385nm.
80wt.% expansion interlamellar spacing microcrystalline graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added and makees
For conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionized water is sufficiently added later
It is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metallic sodium
Electrode assembling becomes button cell to piece as a comparison, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1),
Under the current density of 50mA/g, test loop performance；Battery is tested under the different current density such as 1000mA/g, 2000mA/g
High rate performance.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property:
The high rate performance of battery is tested under 1000mA/g, 2000mA/g etc. different current densities.Test result shows 50mA/g's
Under current density, first circle coulombic efficiency is 69%, and first circle discharge capacity is that 354mA/g is still able to maintain after circulation 100 is enclosed
The specific capacity of 277mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 233mAh/g and
The specific capacity of 188mAh/g.
Embodiment 3
It takes 30g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With technical-grade hydrochloric acid: industrial stage hydrofluoric acid: deionized water volume ratio is that 4:4:2 is made into 100ml mixed acid solution, will
Microlite ink powder pours into the mixed acid solution, carries out heating stirring with magnetic stirring apparatus, whipping temp is 90 DEG C, nitration mixture processing
Time is 12h；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in
Ash impurities in micropore, sonic oscillation time are 20min；Then it uses deionized water filtration washing 3 times again；It is put into baking oven
60 DEG C of heat preservation 6h, the microlite ink powder purified；By obtained micro crystal graphite and 4.2g sodium nitrate, 120g (75mL) dense sulphur
Acid, 15g potassium permanganate mix, and stir 30min in ice-water bath, and it is that 60% hydrogen peroxide solution continues to stir that 70g content, which is then added,
10min is then filtered, and obtained bright yellow solid washs repeatedly, obtains oxidation micro crystal graphite；The oxidation micro crystal graphite that will be obtained
It is mixed with the sodium sulfite solution that 90mL concentration is 0.5mol/L, for 24 hours, filtering, deionized water is repeatedly for magnetic agitation at 50 DEG C
Obtained solid is washed, obtains expanding interlamellar spacing micro crystal graphite, the expansion interlamellar spacing microcrystalline graphite material ratio of embodiment preparation
Surface area is 46.9m2/g；The expansion interlamellar spacing micro crystal graphite interlamellar spacing is 0.380nm.
It weighs 80wt.% N doping manufactured in the present embodiment and is graphitized carbon-coated micro crystal graphite ball material, be added
For 10wt.%Super P as conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, it is ground sufficiently after
A small amount of deionized water is added and is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as survey
Electrode is tried, electrode assembling becomes button cell as a comparison with metallic sodium piece, uses electrolyte system for 1M NaClO4/EC:
DEC (1:1), under the current density of 50mA/g, test loop performance；It is close in the different electric current such as 1000mA/g, 2000mA/g
The high rate performance of the lower test battery of degree.Test result shows that the sodium-ion battery cathode of this example preparation has good electrochemistry
Performance: the high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result shows
Under the current density of 50mA/g, first circle coulombic efficiency is 70%, and first circle discharge capacity is 349mA/g, after circulation 100 is enclosed, still
It is able to maintain the specific capacity of 270mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 228mAh/g and
The specific capacity of 178mAh/g.
Embodiment 4
It takes 40g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With technical-grade hydrochloric acid: industrial stage hydrofluoric acid: deionized water volume ratio is that 5:3:2 is made into 100ml mixed acid solution, will
Microlite ink powder pours into the mixed acid solution, carries out heating stirring with magnetic stirring apparatus, whipping temp is 80 DEG C, nitration mixture processing
Time is 12h；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in
Ash impurities in micropore, sonic oscillation time are 20min；Then it uses deionized water filtration washing 3 times again；It is put into baking oven
60 DEG C of heat preservation 6h, the microlite ink powder purified；By obtained micro crystal graphite and 3.1g sodium nitrate, 100g (62.5mL) dense sulphur
Acid, 10g potassium permanganate mix, and stir 30min in ice-water bath, and it is that 60% hydrogen peroxide solution continues to stir that 60g content, which is then added,
10min is then filtered, and obtained bright yellow solid washs repeatedly, obtains oxidation micro crystal graphite；The oxidation micro crystal graphite that will be obtained
It is mixed with the ferrous sulfite solution that 90mL concentration is 0.5mol/L, the magnetic agitation 36h at 40 DEG C, filtering, deionized water is anti-
The solid that after backwashing is washed obtains expanding interlamellar spacing micro crystal graphite, the expansion interlamellar spacing microcrystalline graphite material of embodiment preparation
Specific surface area is 69.1m2/g；The expansion interlamellar spacing micro crystal graphite interlamellar spacing is 0.374nm.
Using expansion interlamellar spacing microcrystalline graphite material manufactured in the present embodiment, 10wt.%Super P is added as conductive
Agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, ground that a small amount of deionized water mixing shape is sufficiently added later
At uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, using metallic sodium piece as
Comparison electrode is assembled into button cell, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1), in the electricity of 50mA/g
Under current density, test loop performance；The forthright again of battery is tested under the different current density such as 1000mA/g, 2000mA/g
Energy.Test result shows that the sodium-ion battery cathode of this example preparation has good chemical property: close in the electric current of 50mA/g
Under degree, first circle coulombic efficiency is 73%, and first circle discharge capacity is that 252mA/g is still able to maintain 222mA/g's after circulation 100 is enclosed
Specific capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, the specific volume for keeping 198mAh/g and 152mAh/g respectively is remained to
Amount.
Comparative example 1
It takes 20g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With HCl:HF: deionized water is that 5:3:2 is made into 100ml mixed acid solution, and microlite ink powder is poured into the mixed acid solution
In, heating stirring is carried out with magnetic stirring apparatus, whipping temp is 80 DEG C, and the time of nitration mixture processing is 12h；It is filtered with deionized water
Washing 3 times, then carry out sonic oscillation with 100ml dehydrated alcohol and clean, removal remains in the ash impurities in micropore, sonic oscillation
Time is 20min；Then it uses deionized water filtration washing 3 times again；It is put into 60 DEG C of heat preservation 6h, the crystallite purified in baking oven
Graphite powder.
10wt.%Super P is added as conductive agent, 10wt.% carboxylic in the microcrystalline graphite material prepared using this comparative example
Sodium carboxymethylcellulose pyce (CMC) is used as binder, and ground sufficiently a small amount of deionized water, which is added, is mixed to form uniform black later
These slurries are coated in copper foil current collector as test electrode, with metallic sodium piece electrode assembling as a comparison by pasty slurry
As button cell, use electrolyte system for 1M NaClO4/ EC:DEC (1:1) is surveyed under the current density of 50mA/g
Try cycle performance；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result is such as
Under: under the current density of 50mA/g, first circle coulombic efficiency is 55%, and first circle discharge capacity is 35mA/g, 100 circle of circulation
Afterwards, still it is able to maintain the specific capacity of 33mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, 30mAh/g can be kept respectively
With the specific capacity of 25mAh/g.Compared with Example 1, comparative example omits the process of chemical graft and liquid-phase reduction, therefore compares
For the not big interlamellar spacing of the micro crystal graphite of example preparation for sodium ion insertion, this causes material storage sodium capacity very low.
Comparative example 2
It takes 20g micro crystal graphite to be added to crusher and cut broken, then cross 200 mesh mesh screens and sieved to obtain crystallite
Graphite microparticles；With HCl:HF: deionized water is that 5:3:2 is made into 100ml mixed acid solution, and microlite ink powder is poured into the mixed acid solution
In, heating stirring is carried out with magnetic stirring apparatus, whipping temp is 80 DEG C, and the time of nitration mixture processing is 12h；It is filtered with deionized water
Washing 3 times, then carry out sonic oscillation with 100ml dehydrated alcohol and clean, removal remains in the ash impurities in micropore, sonic oscillation
Time is 20min；Then it uses deionized water filtration washing 3 times again；It is put into 60 DEG C of heat preservation 6h, the crystallite purified in baking oven
Graphite powder；By obtained micro crystal graphite and 6g sodium nitrate, 160g (100mL) concentrated sulfuric acid, 25g potassium permanganate is mixed, in ice-water bath
30min is stirred, it is that 60% hydrogen peroxide solution continues to stir 10min that 80g content, which is then added, is then filtered, obtained golden yellow
Solid washs repeatedly, obtains oxidation micro crystal graphite；
The oxidation microcrystalline graphite material prepared using this comparative example, is added 10wt.%Super P as conductive agent,
10wt.% sodium carboxymethylcellulose (CMC) is used as binder, it is ground sufficiently after a small amount of deionized water be added be mixed to form
These slurries are coated in copper foil current collector as test electrode, as a comparison with metallic sodium piece by even black paste slurry
Electrode assembling becomes button cell, uses electrolyte system for 1M NaClO4/ EC:DEC (1:1), it is close in the electric current of 50mA/g
Under degree, test loop performance；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.It surveys
Test result is as follows: under the current density of 50mA/g, first circle coulombic efficiency is 45%, and first circle discharge capacity is 305mA/g, is followed
After ring 100 encloses, it is still able to maintain the specific capacity of 223mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, it can keep respectively
The specific capacity of 101mAh/g and 54mAh/g.Compared with Example 1, comparative example omits the process of liquid-phase reduction, therefore this comparison
The oxidation micro crystal graphite carbon-coating of example preparation is shown in that it is intrinsic that these result in material containing a large amount of intercalated molecule and excessive functional group
It is poor to show as material high rate performance for poorly conductive.
Claims (10)
1. a kind of preparation method for expanding interlamellar spacing micro crystal graphite, it is characterised in that: the following steps are included:
1) micro crystal graphite micro mist is obtained into purifying micro crystal graphite by acid solution purification processes；
2) the purifying micro crystal graphite carries out oxidation intercalation processing, obtains oxidation micro crystal graphite；
3) the oxidation micro crystal graphite by reduction treatment to get.
2. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 1, it is characterised in that: the acid solution
By concentrated hydrochloric acid and dense hydrofluoric acid and water, 0.8~1.5:1:0.5~1.5 are formed by volume.
3. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 1 or 2, it is characterised in that: described
Acid solution purification processes process are as follows: micro crystal graphite micro mist is placed in acid solution, at a temperature of 60~100 DEG C, is handled 10~36 hours.
4. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 1, it is characterised in that: the oxidation
Intercalation process are as follows: purifying micro crystal graphite is mixed with sodium nitrate, the concentrated sulfuric acid and potassium permanganate, is placed in ice-water bath and stirs 30
~40min adds hydrogen peroxide solution and continues 5~15min of stirring, obtains oxidation micro crystal graphite.
5. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 4, it is characterised in that: the crystallite
The mass ratio of graphite and sodium nitrate, the concentrated sulfuric acid, potassium permanganate and 60wt% hydrogen peroxide solution is 20~40:3~6:100~180:
10~30:60~100.
6. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 1, it is characterised in that: the reduction
Treatment process are as follows: oxidation micro crystal graphite is mixed with reducing solution, at a temperature of 40~60 DEG C, stirs 12~36h to get expansion
Big interlamellar spacing micro crystal graphite.
7. a kind of preparation method for expanding interlamellar spacing micro crystal graphite according to claim 6, it is characterised in that: the reduction
Property solution include hydrazine hydrate solution, ascorbic acid solution, sodium sulfite solution, ferrous sulfite, at least one in hydroiodic acid solution
Kind；
The reducing solution concentration is 0.3~5mol/L；
The ratio of the reducing solution and oxidation micro crystal graphite is 3~10mL/g.
8. a kind of expansion interlamellar spacing micro crystal graphite, it is characterised in that: be prepared by any one of claim 1~7 method.
9. a kind of expansion interlamellar spacing micro crystal graphite according to claim 8, it is characterised in that: expand interlamellar spacing micro crystal graphite
Specific surface area be 10~100m2/ g, interlamellar spacing are 0.373~0.394nm.
10. the application of expansion interlamellar spacing microcrystalline graphite material described in claim 8 or 9, it is characterised in that: as sodium ion electricity
Pond negative electrode material application.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707323A (en) * | 2019-09-27 | 2020-01-17 | 太原理工大学 | Anion layer-expanding carbon material and preparation method and application thereof |
| CN112047335A (en) * | 2020-08-31 | 2020-12-08 | 湖南宸宇富基新能源科技有限公司 | Combined treatment method for black powder of waste lithium ion battery |
| WO2021097539A1 (en) * | 2019-11-21 | 2021-05-27 | International Graphite Ltd | Process and apparatus for producing high purity graphite |
| CN114122373A (en) * | 2021-11-17 | 2022-03-01 | 内蒙古恒胜新能源科技有限公司 | Preparation method of natural graphite silicon carbon negative electrode material and lithium ion battery |
| CN115425225A (en) * | 2022-08-31 | 2022-12-02 | 广东凯金新能源科技股份有限公司 | Purification method of microcrystalline graphite negative electrode material for lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311431A1 (en) * | 2010-06-17 | 2011-12-22 | Samsung Sdi Co., Ltd. | Crystalline carbonaceous material with controlled interlayer spacing and method of preparing same |
| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
| CN104477887A (en) * | 2014-11-25 | 2015-04-01 | 北京理工大学 | Method for preparing graphene from microcrystalline graphite |
| CN105502374A (en) * | 2016-01-30 | 2016-04-20 | 山西大学 | Preparation method for small graphene |
| CN105720269A (en) * | 2016-03-04 | 2016-06-29 | 深圳市翔丰华科技有限公司 | Preparation method of large-layer-spacing graphite anode material of sodium-ion battery |
-
2018
- 2018-12-05 CN CN201811476835.9A patent/CN109592677B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311431A1 (en) * | 2010-06-17 | 2011-12-22 | Samsung Sdi Co., Ltd. | Crystalline carbonaceous material with controlled interlayer spacing and method of preparing same |
| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
| CN104477887A (en) * | 2014-11-25 | 2015-04-01 | 北京理工大学 | Method for preparing graphene from microcrystalline graphite |
| CN105502374A (en) * | 2016-01-30 | 2016-04-20 | 山西大学 | Preparation method for small graphene |
| CN105720269A (en) * | 2016-03-04 | 2016-06-29 | 深圳市翔丰华科技有限公司 | Preparation method of large-layer-spacing graphite anode material of sodium-ion battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707323A (en) * | 2019-09-27 | 2020-01-17 | 太原理工大学 | Anion layer-expanding carbon material and preparation method and application thereof |
| WO2021097539A1 (en) * | 2019-11-21 | 2021-05-27 | International Graphite Ltd | Process and apparatus for producing high purity graphite |
| CN112047335A (en) * | 2020-08-31 | 2020-12-08 | 湖南宸宇富基新能源科技有限公司 | Combined treatment method for black powder of waste lithium ion battery |
| CN114122373A (en) * | 2021-11-17 | 2022-03-01 | 内蒙古恒胜新能源科技有限公司 | Preparation method of natural graphite silicon carbon negative electrode material and lithium ion battery |
| CN114122373B (en) * | 2021-11-17 | 2023-12-01 | 内蒙古恒胜新能源科技有限公司 | Preparation method of natural graphite silicon-carbon negative electrode material and lithium ion battery |
| CN115425225A (en) * | 2022-08-31 | 2022-12-02 | 广东凯金新能源科技股份有限公司 | Purification method of microcrystalline graphite negative electrode material for lithium ion battery |
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