CN107658464A - Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery - Google Patents
Preparation method for phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite of lithium ion battery Download PDFInfo
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Abstract
Present invention relates particularly to the preparation method of the phosphoric acid vanadium lithium for lithium ion battery/expansion micro crystal graphite/carbon composite, lithium compound, vfanadium compound and the phosphate of solubility are added in deionized water according to proper proportion and prepare solution, then adds citric acid and expansion micro crystal graphite.Then carbon-based be placed in mixed liquor that surface attachment has vfanadium compound is impregnated a couple of days, takes out the carbon-based drying after dipping, then carry out high-temperature calcination for a period of time under protective atmosphere, it is rear to take out cooling；Repeat the above steps, finally low-temperature carbonization processing and high―temperature nuclei processing successively again, phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material is obtained in matrix surface.It is raw material that composite of the present invention, which has used expansion micro crystal graphite cheap and easy to get to substitute graphene, obtained composite has excellent chemical property, in the case where keeping charging and discharging capacity not drop, has more preferable cyclical stability, high financial profit, it is adapted to industrial applications.
Description
Technical field
The invention belongs to the technical field of battery electrode composites, more particularly to the phosphorus for lithium ion battery
The preparation method of sour vanadium lithium/expansion micro crystal graphite/carbon composite.
Background technology
Since Goodenough etc. proposes polyanion lithium electricity LiFePO 4 of anode material first, researcher is to poly- the moon
Iron phosphate expands numerous studies, wherein being exactly the most successfully the industrial metaplasia for realizing lithium iron phosphate positive material
Production, and research report of the people to phosphoric acid vanadium lithium is not a lot, and industrialized production is still not implemented at present.But phosphoric acid vanadium lithium is performance
A kind of material more excellent than LiFePO4, has advantages below：A, it has excellent heat endurance, what is studied at present
LiFePO 4 is only slightly lower than in positive electrode；B, there are high discharge voltage and multiple discharge voltage plateaus, average discharge volt
For 4.1 V, higher than 3.4 V discharge voltages of LiFePO 4, and there are 4 electric discharges of 3.5V, 3.6V, 4.1V and 4.6V flat
Platform；C, excellent cyclical stability and high discharge capacity, theoretical capacity 197mAh/g, higher than LiFePO 4 170mAh/g
Theoretical capacity.As can be seen that the research space of phosphoric acid vanadium lithium is very big.
The synthetic method of lithium vanadium phosphate/graphene composite material has a variety of at present, and graphene is by sp2The carbon atom of hydridization
The two dimensional crystal of composition, there is good electric conductivity, big specific surface area.The excellent electric property of graphene makes it suitable as
Conductive additive.By both compound, methods that LiFePO4/graphene/carbon composite material can be prepared, but stone is prepared now
Black alkene cost is too high, while Chinese graphene yield is not high, and the combination electrode material performance being prepared using graphene is not
There is king-sized lifting, so making phosphoric acid vanadium lithium/graphene combination electrode material be difficult to carry out commercial application.
Micro crystal graphite is up to 2,000,000,000 tons in China's reserves, and for the crystal of micro crystal graphite in aggregate is inlayed, particle is small, electricity
Visible morphon under sub- microscope, there is good chemical property, but the utilization of a large amount of micro crystal graphites belongs to now
Low value-added utilization, expansion micro crystal graphite carries out expanded on the basis of micro crystal graphite, and specific surface area greatly increases, electrochemistry
Can be more excellent, we can attempt to replace graphene to prepare combination electrode material with expanded graphite to obtain more preferable compound electric
Pole material.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided one kind is simple and environmentally-friendly, structure is steady
The fixed, phosphoric acid vanadium lithium for lithium ion battery/expansion micro crystal graphite/carbon composite of good cycle, low production cost
Preparation method, it is raw material that the combination electrode material, which has used expansion micro crystal graphite cheap and easy to get to substitute graphene, in matrix
Upper to be combined to be formed with phosphoric acid vanadium lithium, obtained composite has excellent chemical property, is keeping charging and discharging capacity
In the case of not dropping, there is more preferable cyclical stability, high financial profit, be adapted to industrial applications.
The purpose of the present invention is achieved by the following technical programs：
The preparation method of phosphoric acid vanadium lithium for lithium ion battery/expansion micro crystal graphite/carbon composite, including following step are provided
Suddenly：
A kind of preparation method of phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material, comprises the following steps：
S1. it is 3 according to the atomic ratio of lithium, vanadium, phosphorus by the lithium compound, vfanadium compound, phosphate of solubility:2:3 mixing are placed in
In deionized water, while appropriate citric acid and expansion micro crystal graphite are added, be sufficiently stirred to form mixed liquor at a certain temperature；
S2. surface attachment have vfanadium compound it is carbon-based lay flat on one's back to be placed in mixed liquor obtained by step S1 impregnate a couple of days, take out leaching
Carbon-based drying after stain, then carry out high-temperature calcination for a period of time under protective atmosphere, it is rear to take out cooling；
S3. as object, repeat step S1, S2 is no less than 2 times the matrix after being cooled down using calcining；
S4. matrix obtained by step S3 is carried out into low-temperature carbonization processing and high―temperature nuclei successively under protective atmosphere to handle, in base
Body surface face obtains phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material.
The metallic matrix that surface attachment is had to vfanadium compound of the invention is placed in containing lithium ion, vanadium ion, phosphorus
Impregnate a couple of days in the mixed solution of ion, sodium citrate and graphene oxide, in mixed solution, while carry out three groups of reactions, lithium
Ion, vanadium ion, phosphonium ion react, and citric acid and lithium ion, vanadium ion, phosphonium ion react, then micro- with expansion
Spar ink generation is compound, and final three groups of reactions can form preliminary composite, after matrix immerses mixed liquor, metal base surface
The vfanadium compound of attachment can be used as crystal seed, make composite seed surrounding growth, change big, until the excellent composite wood of forming properties
Material, the phosphoric acid vanadium lithium formed/expansion micro crystal graphite/carbon composite superior performance, while the preparation method technique of the present invention
Simply, easily operation, cost are relatively low.
Preferably, micro crystal graphite is expanded in step S1 to be prepared using high-temperature expansion method by micro crystal graphite.
Preferably, the mass fraction after citric acid described in step S1 adds is 10 ~ 15%, and the expansion micro crystal graphite adds
Mass fraction after entering is 5 ~ 10%, and 0.5 ~ 2h is stirred under 70 ~ 90oC of temperature.
Preferably, the carbon-based number of days impregnated in mixed liquor that surface attachment described in step S2 has vfanadium compound is 3 ~ 5 days.
Preferably, high-temperature calcination is carried out in tube furnace described in step S2, and temperature is 800 ~ 1000 DEG C, and calcination time is
0.5 ~ 1h, protective atmosphere are nitrogen.
Preferably, in step S4, the low-temperature carbonization processing design parameter is：1 ~ 2h of low-temperature carbonization at 500 ~ 580 DEG C,
The low-temperature carbonization 1.5h preferably at 550 DEG C；The high―temperature nuclei handles design parameter：The high―temperature nuclei 2 at 850-950 DEG C
~ 3h, the high―temperature nuclei 2.5h preferably at 900 DEG C.
Preferably, the carbon-based preparation method that the surface attachment has vfanadium compound is：By appropriate vfanadium compound and pure water
Solution or suspension are mixed to form, using the form of spraying by above-mentioned solution or suspension even application in matrix surface, so
Afterwards being coated with the carbon-based vacuum drying of vanadium solution, then it is placed in tube furnace, is forged under certain temperature in protective atmosphere
Burn certain time.
Preferably, the vfanadium compound is V on matrix2O5、NH4VO3、V2O3One or more, the vfanadium compound system
It is 0.1 ~ 0.15mmol/ml into the concentration of the aqueous solution or suspension.
Preferably, the vacuum drying concrete operations are that matrix is placed in into the vacuum drying chamber that temperature is 110 DEG C ~ 120 DEG C
Middle drying 1 ~ 5 hour.
Preferably, calcining heat is 300 ~ 600 DEG C in tube furnace, and the time is 1 ~ 2 hour, and the protective gas is nitrogen.
Compared with prior art, the advantage of the invention is that：
（1）The phosphoric acid vanadium lithium that the present invention synthesizes/expansion micro crystal graphite/carbon composite electrode material has used expansion cheap and easy to get
It is raw material that micro crystal graphite, which substitutes graphene, is combined to be formed with phosphoric acid vanadium lithium on matrix, obtained composite has excellent
Chemical property, keeping in the case that charging and discharging capacity do not drop, there is more preferable cyclical stability, high financial profit,
It is adapted to industrial applications.Meanwhile the synthesis combination electrode material has multi-pore channel feature, this structure can allow electrolyte to be easy to
Come in, increase the contact area of electrolyte and composite, substantially reduce the transmission path of lithium ion, improve lithium from
The efficiency of transmission of son, so as to obtain good chemical property.
（2）Prepare surface have vfanadium compound it is carbon-based when, vfanadium compound is prepared the aqueous solution by the invention, lead to
Spray-on process is crossed by the aqueous solution even application of vfanadium compound in matrix surface, the vfanadium compound as crystalline substance of these matrix surfaces
Kind, when matrix is immersed in mixed solution, the presence of these crystal seeds is not only beneficial to the formation of phosphoric acid vanadium lithium crystal, also makes to be formed
It is evengranular be distributed on matrix, so as to formed composite performance it is more superior.
（3）The present invention prepares expansion microcrystalline graphite material using micro crystal graphite, is further used as preparing phosphoric acid vanadium lithium/expansion
A kind of raw material of micro crystal graphite/carbon composite electrode material, there is provided new application of micro crystal graphite.
（4）The present invention combines traditional high-temperature expansion method and graphite expansion stove in high-temperature expansion processing procedure, uses
Optimal expansion temperature, and the stabilization of product can be effectively improved by the control to raw material and technological parameter around expansion temperature
Property, so as to prepare the expansion micro crystal graphite that expansion multiple is 210.
（5）Phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material discharge and recharge under 5C multiplying powers of gained of the invention
When, first discharge specific capacity reaches as high as 160mAh/g at room temperature；After 50 circulations, capability retention is up to 97.3
%。
Brief description of the drawings
Fig. 1 is the high temperature graphite expansion furnace structure figure of embodiment 1.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
Expansion micro crystal graphite used is prepared using following methods in all embodiments of the invention：
S11. micro crystal graphite raw material, phosphorus content 70%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S12. microlite ink powder obtained by step S11 is placed in reaction unit with perchloric acid and potassium permanganate and carries out chemistry for the first time
Intercalation processing, inflatable micro crystal graphite acidic suspension is obtained, the filtering of micro crystal graphite acidic suspension is may expand to gained, is retained
Filtrate is standby, then washs filtrate, dries, obtains and once may expand micro crystal graphite；Wherein, first time chemical graft
Concretely comprise the following steps：S121. it is 10 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S122. press
The mass ratio of micro crystal graphite powder and strong oxidizer is 2：1 adds strong oxidizer, after being stirred at room temperature uniformly, is warming up to 30 DEG C
Continue stirring reaction 3h；S23. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, is further continued for stirring reaction 3h；
S13. micro crystal graphite will be once may expand obtained by step S12 to be placed in graphite expansion stove, is carried out first time high-temperature expansion, is obtained
To once expanding micro crystal graphite；Wherein first time high-temperature expansion concretely comprises the following steps：S131. feed：, will using conserving graphite expanding furnace
Expansible graphite is put into burner hearth by charging aperture, and the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S132.
Expansion：The expansion temperature of burner hearth is 800 DEG C, by controlled wind speed come to control Bulking Time be 5s；S133. discharge：Complete step
After S52, discharging opening temperature is 50 DEG C, then collects to obtain an expanded graphite in discharge outlet；
S14. will once expand micro crystal graphite obtained by step S13 to mix with nitric acid, gained filtrate is mixed after then filtering with step S12
Unify to be placed in reaction unit and reacted, obtained inflatable micro crystal graphite acidic suspension, microlite may expand to gained
Black acidic suspension filtering, washing, dry, obtain secondary inflatable micro crystal graphite；Wherein, the specific steps of second of chemical graft
For：S141. an expanded graphite obtained by step S13 is mixed with nitric acid, nitric acid amount is according to the liquid with once expanding micro crystal graphite
Gu than being 1：1L/Kg is added；S142. gained filtrate after step S12 is filtered is added, 60 DEG C is warming up to and continues stirring reaction 1h；
S143. adding deionized water makes the temperature in reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h；
S15. secondary inflatable micro crystal graphite obtained by step S14 is placed in graphite expansion stove, carries out second of high-temperature expansion,
Obtain reexpansion micro crystal graphite；Wherein first time high-temperature expansion concretely comprises the following steps：S151. feed：Using conserving graphite expanding furnace,
Expansible graphite is put into burner hearth by charging aperture, the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；
S152. expand：The expansion temperature of burner hearth is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；S153. discharge：Complete
After step S152, discharging opening temperature is 50 DEG C, then collects to obtain expansion micro crystal graphite in discharge outlet.
After testing, the expansion multiple of gained expansion micro crystal graphite is 210, is wormlike porous material, pore size distribution range
For 1~100nm, specific surface area 302m2/ g, resistivity are 9.78 × 10-4Ω•m。
Embodiment 2
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.1 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in stainless steel base in vacuum drying chamber that 4 are dried at 80 DEG C is small to uniformly spraying on Oroxylum indicum matrix
When, then Oroxylum indicum matrix is placed in tube furnace, in nitrogen atmosphere, 300 DEG C calcine 2 hours, obtaining surface has V2O5Oroxylum indicum
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
10% citric acid and 5% expansion micro crystal graphite is added, is placed on magnetic stirring apparatus and 0.5h formation mixed solutions is stirred at 70 DEG C；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in mixed solution obtained by step S1, to be impregnated 3 days, takes out dipping
Matrix afterwards, which is placed in vacuum drying chamber, dries, and is then put into tube furnace and 1000 degree of calcinings are carried out under nitrogen protection atmosphere
0.5h, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S2 2 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical nitrogen carries out low-temperature carbonization 2h in 500 DEG C, then heat to
850 DEG C of progress high―temperature nuclei 2h, the phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material finally obtained.
The phosphoric acid vanadium lithium of gained/expansion micro crystal graphite/carbon composite electrode material is first at room temperature under 5C multiplying powers during discharge and recharge
Secondary specific discharge capacity is up to 150mAh/g；After 50 circulations, capability retention is 94.9 %.
Embodiment 3
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.1 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in rush matrix in vacuum drying chamber that 5 are dried at 80 DEG C is small to uniformly spraying on rush matrix
When, then rush matrix is placed in tube furnace, in nitrogen atmosphere, 300 DEG C calcine 8 hours, obtaining surface has V2O5Rush
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
10% citric acid and 7% expansion micro crystal graphite is added, is placed on magnetic stirring apparatus and 0.5h formation mixed solutions is stirred at 80 DEG C；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in mixed solution obtained by step S1, to be impregnated 4 days, takes out dipping
Matrix afterwards, which is placed in vacuum drying chamber, dries, and is then put into tube furnace and 1000 degree of calcinings are carried out under nitrogen protection atmosphere
0.5h, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S2 3 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical nitrogen carries out low-temperature carbonization 1.5h in 550 DEG C, then heat to
880 DEG C of progress high―temperature nuclei 2.5h, the phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material finally obtained.
The phosphoric acid vanadium lithium of gained/expansion micro crystal graphite/carbon composite electrode material is first at room temperature under 5C multiplying powers during discharge and recharge
Secondary specific discharge capacity is up to 160mAh/g；After 50 circulations, capability retention is 97.3 %.
Embodiment 4
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.1 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in rush matrix in vacuum drying chamber that 1 is dried at 120 DEG C is small to uniformly spraying on rush matrix
When, then rush matrix is placed in tube furnace, in nitrogen atmosphere, 400 DEG C calcine 1 hour, obtaining surface has V2O5Rush
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
15% citric acid and 8% expansion micro crystal graphite is added, is placed on magnetic stirring apparatus and 0.5h formation mixed solutions is stirred at 80 DEG C；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in mixed solution obtained by step S1, to be impregnated 5 days, takes out dipping
Matrix afterwards, which is placed in vacuum drying chamber, dries, and is then put into tube furnace and 1000 degree of calcinings are carried out under nitrogen protection atmosphere
1h, it is rear to take out cooling；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S2 4 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical nitrogen carries out low-temperature carbonization 1h in 530 DEG C, then heat to
900 DEG C of progress high―temperature nuclei 2h, the phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material finally obtained.
The phosphoric acid vanadium lithium of gained/expansion micro crystal graphite/carbon composite electrode material is first at room temperature under 5C multiplying powers during discharge and recharge
Secondary specific discharge capacity is up to 149mAh/g；After 50 circulations, capability retention is 95.1 %.
Embodiment 5
There is V on surface2O5Matrix preparation：By V2O5It is dissolved in pure water and prepares 0.1 mmol/ml V2O5The aqueous solution, with simple
Then sprayer unit is placed in Oroxylum indicum matrix in vacuum drying chamber that 2 are dried at 80 DEG C is small to uniformly spraying on Oroxylum indicum matrix
When, then Oroxylum indicum matrix is placed in tube furnace, in nitrogen atmosphere, 600 DEG C calcine 1 hour, obtaining surface has V2O5Oroxylum indicum
Matrix.
S1, by mol ratio be 3:1:3 lithium acetate, vanadic anhydride and ammonium dihydrogen phosphate is dissolved in deionized water, then
15% citric acid and 10% graphene oxide is added, is placed on magnetic stirring apparatus and 0.5h formation mixed solutions is stirred at 90 DEG C；
S2, the matrix that there is vanadic anhydride on surface, which lay flat on one's back to be placed in mixed solution obtained by step S1, to be impregnated 4 days, takes out dipping
Matrix afterwards, which is placed in vacuum drying chamber, dries, and is then put into tube furnace and 900 degree of calcining 1h are carried out under nitrogen protection atmosphere,
Cooling is taken out afterwards；
Matrix after calcining cooling obtained by S3, step S2 is object, repeat step S1, S2 2 times；
S4, matrix obtained by step S3 is placed in the tube furnace of logical nitrogen carries out low-temperature carbonization 2h in 580 DEG C, then heat to
950 DEG C of progress high―temperature nuclei 3h, the phosphoric acid vanadium lithium/graphene/carbon combination electrode material finally obtained.
The phosphoric acid vanadium lithium of gained/graphene/carbon combination electrode material during discharge and recharge, discharges first at room temperature under 5C multiplying powers
Specific capacity is up to 130mAh/g；After 50 circulations, capability retention is 94.3 %.
Embodiment 6
Referring to Fig. 1, the graphite expansion stove that is used for embodiment 1 first time high-temperature expansion and second of high-temperature expansion process, graphite
Expansion furnace includes body of heater 1, feeding device 2, drawing mechanism 3 and control device, and raw material passes through feeding device 2 to body of heater 1, Ran Houtong
Drawing mechanism 3 is crossed to collect；Drawing mechanism 3 is located above body of heater, and feeding device 2 is located at below body of heater；Heating dress is provided with body of heater 1
11 are put, using Resistant heating, the inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas 41, airflow line
42 and control damper 43, source of the gas 41 is air, and connects airflow line 42, and airflow line 42 connects air-flow shower nozzle 4, air-flow control
Valve 43 processed is located in airflow line 42, and the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically using feed screw, control device
Including processor 5 and controller, processor 5 is provided with and control panel and be connected with controller, controller including the first controller 53,
The controller 51 of second controller 52 and the 3rd, the first controller 53 are connected with the control damper 43 of air-flow shower nozzle 4, the second control
Device 52 is connected with feeding device 2, and the 3rd controller 51 is connected with heater 11；
Wherein, processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller is using charging
Valve-driving circuit, the 3rd controller use heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes heat exchanger tube 71 and water cooling tube 72,
One end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and horizontal angle are 45 DEG C~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71, and is provided with
Cyclone separator 33, the other end are connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with reserves storehouse
31 connections；Connecting pipe and 32 horizontal angles are 45 DEG C~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, is coordinated by motor and ball-screw so that stir
Mix device 8 and upper and lower linear motion is done in body of heater 1, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and heater 6 also is provided with to control in charging aperture
The temperature of charging aperture processed, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
Can control time and the temperature of expansion by control panel, specifically processor by control the first controller and
Second controller controls air velocity and charging rate, so as to control the reaction time that intercalated graphite expands, the 3rd controller
The temperature of heater can be controlled, the intellectuality of graphite expansion is realized, reaches and be precisely controlled.
Graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchanger tube and connection from the bottom up
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve anti-
Yield is answered, while also solves space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensure that intercalation stone
Ink is heated evenly, so as to which the expanded reaction efficiency of intercalated graphite be significantly increased.
Inventor states that the present invention illustrates the detailed process equipment of the present invention and technological process, but this by above-described embodiment
Invention is not limited to above-mentioned detailed process equipment and technological process, that is, does not mean that the present invention has to rely on above-mentioned detailed process
Equipment and technological process could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to this
The equivalence replacement of each raw material of invention product and the addition of auxiliary element, the selection of concrete mode etc., all fall within the protection of the present invention
Within the scope of scope and disclosure.
Claims (10)
1. the preparation method of phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite for lithium ion battery, it is characterised in that
Comprise the following steps：
S1. it is 3 according to the atomic ratio of lithium, vanadium, phosphorus by the lithium compound, vfanadium compound, phosphate of solubility:2:3 mixing are placed in
In deionized water, while appropriate citric acid and expansion micro crystal graphite are added, be sufficiently stirred to form mixed liquor at a certain temperature；
S2. surface attachment have vfanadium compound it is carbon-based lay flat on one's back to be placed in mixed liquor obtained by step S1 impregnate a couple of days, take out leaching
Carbon-based drying after stain, then carry out high-temperature calcination for a period of time under protective atmosphere, it is rear to take out cooling；
S3. as object, repeat step S1, S2 is no less than 2 times the matrix after being cooled down using calcining；
S4. matrix obtained by step S3 is carried out into low-temperature carbonization processing and high―temperature nuclei successively under protective atmosphere to handle, in base
Body surface face obtains phosphoric acid vanadium lithium/expansion micro crystal graphite/carbon composite electrode material.
2. the preparation method of composite according to claim 1, it is characterised in that micro crystal graphite is expanded in step S1 by micro-
Spar ink is prepared using high-temperature expansion method.
3. the preparation method of composite according to claim 1, it is characterised in that after citric acid described in step S1 adds
Mass fraction be 10 ~ 15%, it is described expansion micro crystal graphite add after mass fraction be 5 ~ 10%, in temperature 70 ~ 90oStirred under C
Mix 0.5 ~ 2h.
4. the preparation method of composite according to claim 1, it is characterised in that surface attachment described in step S2 has vanadium
The carbon-based number of days impregnated in mixed liquor of compound is 3 ~ 5 days.
5. the preparation method of composite according to claim 1, it is characterised in that high-temperature calcination is in tubular type described in step S2
Carried out in stove, temperature is 800 ~ 1000 DEG C, and calcination time is 0.5 ~ 1h, and protective atmosphere is nitrogen.
6. the preparation method of composite according to claim 1, it is characterised in that in step S4, at the low-temperature carbonization
Managing design parameter is：1 ~ 2h of low-temperature carbonization at 500 ~ 580 DEG C, the low-temperature carbonization 1.5h preferably at 550 DEG C；The high temperature closes
It is into processing design parameter：2 ~ 3h of high―temperature nuclei at 850-950 DEG C, the high―temperature nuclei 2.5h preferably at 900 DEG C.
7. according to the preparation method of any one of claim 1 ~ 6 composite, it is characterised in that the surface attachment has vanadium
The carbon-based preparation method of compound is：Appropriate vfanadium compound and pure water are mixed to form solution or suspension, using spraying
Form by above-mentioned solution or suspension even application in matrix surface, then the carbon-based vacuum for being coated with vanadium solution
Drying, then be placed in tube furnace, certain time is calcined under certain temperature in protective atmosphere.
8. the preparation method of composite according to claim 7, it is characterised in that the vfanadium compound is V on matrix2O5、
NH4VO3、V2O3One or more, it is 0.1 ~ 0.15mmol/ that the aqueous solution or the concentration of suspension, which is made, in the vfanadium compound
ml。
9. the preparation method of composite according to claim 7, it is characterised in that the vacuum drying concrete operations be by
Matrix is placed in the vacuum drying chamber that temperature is 110 DEG C ~ 120 DEG C and dried 1 ~ 5 hour.
10. the preparation method of composite according to claim 7, it is characterised in that in tube furnace calcining heat be 300 ~
600 DEG C, the time is 1 ~ 2 hour, and the protective gas is nitrogen.
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