CN108987687A - A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof - Google Patents
A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low-temperature lithium ion battery graphite cathode materials and preparation method thereof.The low-temperature lithium ion battery graphite cathode material includes the fast-ionic conductor of graphite and Graphite Coating；The oxidation-reduction potential of the fast-ionic conductor is higher than graphite.Preparation method are as follows: wet ball grinding is carried out to original graphite powder, mixed liquor is dried to powder using spray dryer, the graphite powder for obtaining smaller particle carries out surface cladding after carrying out intercalation to graphite powder, obtains the graphite cathode material for being used for low-temperature lithium ion battery.In this negative electrode material structure, it can control graphite partial size, shorten lithium ion diffusion length, graphite layers can be obviously improved low temperature lower electrode material ion-diffusibility away from increase after intercalation, and the metal or high conductivity substance of graphite layers insertion can improve whole electric conductivity, cladding fast-ionic conductor is carried out in graphite surface, the SEI film of stable and uniform can be generated, improve lithium ion diffusivity, improve interface performance under low temperature.The material is alternatively arranged as a kind of ideal anode material of lithium-ion battery and high-performance super capacitor material.
Description
Technical field
The present invention relates to field of lithium ion battery material, more particularly to a kind of low-temperature lithium ion battery graphite cathode material
Preparation method and application.
Background technique
At present the problem of environmental pollution is getting worse, and the burning for reducing fossil fuel is today's society urgent need to resolve it
One.The lithium ion battery technology of high-energy density high power density is because of its answering in hybrid vehicle and electric car field
Cause extensive concern in the past few years with potentiality.As commercialized graphite cathode material in charging, Li+It is embedded in graphite
When material, desolvation is first had to, this process can consume certain energy, hinder Li+It is diffused into inside graphite；And low
Under temperature, SEI membrane impedance is larger, and the kinetic characteristics of graphite cathode are deteriorated, especially during the charging process, the activation polarization of cathode
Obvious aggravation is easy precipitating metal lithium and forms Li dendrite, wears out diaphragm and causes positive and negative anodes short-circuit, causes security risk.
It is current to be coated for the graphite modified research of low temperature mainly surface, one layer of soft carbon of cladding or hard on graphite powder surface
The materials such as carbon or lithium titanate improve its interface performance.However the methods of this is not for lithium ion diffusivity under low temperature
It makes improvements.
Summary of the invention
The present invention provides a kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof, which is used as low temperature
Lower lithium ion battery negative material has preferable chemical property, and the preparation method of material is simple, easily operated, is easy to work
Industry metaplasia produces.
A kind of low-temperature lithium ion battery graphite cathode material of the present invention: the low-temperature lithium ion battery graphite cathode material packet
Include the fast-ionic conductor of graphite and Graphite Coating；The oxidation-reduction potential of the fast-ionic conductor is higher than graphite.
Preferably, a kind of low-temperature lithium ion battery graphite cathode material of the present invention；The low-temperature lithium ion battery
Graphite cathode material is made of the fast-ionic conductor of intercalated graphite, graphite layers conductive material and Graphite Coating.
A kind of low-temperature lithium ion battery graphite cathode material of the present invention；The graphite layers conductive material is being sintered by intercalation object
It is transformed in the process；The intercalation object is selected from least one of aniline, pyrroles, pink salt, cobalt salt, molysite, nickel salt, manganese salt；
The pink salt is selected from least one of the chlorate of tin, the acetate of tin, the sulfate of tin, the nitrate of tin；
The cobalt salt is selected from least one of the chlorate of cobalt, the acetate of cobalt, the sulfate of cobalt, the nitrate of cobalt；
The molysite is selected from least one of the chlorate of iron, the acetate of iron, the sulfate of iron, the nitrate of iron；
The nickel salt is selected from least one of the chlorate of nickel, the acetate of nickel, the sulfate of nickel, the nitrate of nickel；
The manganese salt is selected from least one of the chlorate of manganese, the acetate of manganese, the sulfate of manganese, the nitrate of manganese.
Industrially in application, pink salt, cobalt salt, molysite, nickel salt, manganese salt are directly translated into corresponding metal after sintering.Aniline, pyrroles
It is directly translated into conductive carbon after sintering.
Preferably, the graphite layers conductive material is selected from least one of zeroth order tin, zeroth order cobalt, zero-valent nickel.
A kind of low-temperature lithium ion battery graphite cathode material of the present invention；The fast-ionic conductor includes LiM2(PO4)3And/or
With LiM2(PO4)3For a series of doped products of parent, the M is selected from least one of Zr, Sc, Ti, Ge；Wherein adulterate
Element is selected from least one of Si, Al, La, Mg, Zn, Sn, Fe, Mn, Co, Ni, Cu, W, Mo, V, Cr.
A kind of low-temperature lithium ion battery graphite cathode material of the present invention；The fast-ionic conductor is coated on graphite surface and is formed
A layer thickness is the clad of 1-10nm.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention；Include the following steps:
Using intercalated graphite as raw material；Lithium source, the source M, doped chemical, phosphorus source will be added after intercalated graphite wiring solution-forming；Using
Hydro-thermal method or solvent-thermal method coat one layer of fast-ionic conductor in intercalated graphite；Then washed, dry, sintering obtains described
Low-temperature lithium ion battery graphite cathode material；The source M provides at least one of Zr, Sc, Ti, Ge of non-zero valence element；Institute
It states doped chemical and is selected from least one of Si, Al, La, Mg, Zn, Sn, Fe, Mn, Co, Ni, Cu, W, Mo, V, Cr.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, when the source M is titanium source；The titanium source
For butyl titanate or isopropyl titanate.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, phosphorus source are selected from diammonium hydrogen phosphate, phosphorus
At least one of acid dihydride ammonium, phosphoric acid.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, lithium source are selected from lithium hydroxide, carbonic acid
At least one of lithium, lithium acetate, lithium nitrate.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention will add after intercalated graphite wiring solution-forming
After entering lithium source, the source M, doped chemical, phosphorus source, intercalated graphite composite material solution is obtained；The intercalated graphite composite material solution
In, lithium, M, phosphorus molar ratio be 1-1.5:2:3-4；The mass ratio of the M and graphite in intercalated graphite is 1-20:100；Doping
The molar ratio of element and M are 0-5:10；
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, hydro-thermal method or solvent-thermal method are in intercalation
It is 6~48h controlled at 160~230 DEG C, time when coating one layer of fast-ionic conductor on graphite.Hydro-thermal method is in intercalated graphite
When one layer of fast-ionic conductor of upper cladding, solvent is at least one of deionized water or dehydrated alcohol, ethylene glycol, acetone and water group
At mixture.Solvent-thermal method in intercalated graphite coat one layer of fast-ionic conductor when, solvent be selected from dehydrated alcohol, ethylene glycol,
At least one of acetone.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, the detergent be ethyl alcohol or go from
Sub- water, number are 2-6 times.Drying temperature be 60~150 DEG C, the time be 6~for 24 hours；
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, when the sintering, using protection gas
Atmosphere sintering；The protective atmosphere is selected from one of argon atmosphere, nitrogen atmosphere, vacuum atmosphere.Heating rate is controlled when sintering
For 1~10 DEG C/min, sintering temperature is 600~900 DEG C, soaking time at a sintering temperature is 4~for 24 hours.
Preferably, a kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention；The intercalation
Graphite is prepared by following step:
Step 1
Graphite powder is added to progress wet process stirring ball-milling in ball mill, mixed solution is spray-dried；
Step 2
After graphite powder obtained by step 1 is mixed with concentrated acid, graphite oxide is obtained after ultrasonic agitation, centrifugal drying；
Step 3
Graphite oxide wiring solution-forming obtained in step 2 is added intercalation object and reducing agent, washes solution after ultrasonic disperse
Filtering is washed, filtration product is heat-treated to obtain intercalated graphite material.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, the choosing of ball milling solvent described in step 1
It is selected as deionized water or dehydrated alcohol；After solvent is added, slurry is constituted, mass content of graphite is 30~70% in slurry.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, graphite powder described in step 1 are day
One kind of right graphite, artificial graphite or carbonaceous mesophase spherules；Its partial size is 30-100 microns.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, Ball-milling Time 4- described in step 1
For 24 hours, the revolving speed of ball milling is 200-400r/min；Using inlet air temperature when spray dryer be 200-300 DEG C, leaving air temp is
100-150℃；The granularity that graphite is made is 1-20um.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, concentrated acid described in step 2 are hydrochloric acid
Or one kind of nitric acid, concentrated acid concentration are 0.5-3mol/L；3-24h is stirred by ultrasonic；Drying temperature is at 60-200 DEG C.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, intercalation object described in step 3 are benzene
Amine, pyrroles or metallic tin, cobalt, iron, nickel and manganese chlorate, acetate, sulfate, nitrate.Intercalation object is during the sintering process
It is converted to graphite layers conductive material.
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, reducing agent described in step 3 are water
Close hydrazine, D-araboascorbic acid sodium, sodium sulfite, azanol or sodium borohydride；
A kind of preparation method of low-temperature lithium ion battery graphite cathode material of the present invention, ultrasonic disperse 1- described in step 3
12h；Solution is washed to pH value 6-8；Tube furnace heating rate is 1-10 DEG C/min, and temperature is 180-600 DEG C, time 2-12h；Gas
Atmosphere in argon atmosphere, nitrogen atmosphere, argon nitrogen atmosphere, carbon dioxide atmosphere, hydrogen atmosphere, nitrogen dioxide atmosphere at least one
Kind.
Of the invention designed and preparation low-temperature lithium ion battery graphite cathode material；After being assembled into battery, 0.2C's
200 circle capacity retention rates are recycled under discharging condition, at -20 DEG C is more than or equal to 94%.200 circle capacity of circulation retains at -40 DEG C
Rate is more than or equal to 93%.
Principle and advantage
The diffusion and graphite partial size of lithium ion have direct relation, and ball-milling method is most common reduction agent particle size
One of method graphite layers can be expanded away from improving lithium ion diffusivity, and in Intercalation reaction by intercalated graphite
The high conductive material such as metal, conductive carbon can greatly enhance graphite ability.Fast-ionic conductor has energy and liquid electric
The comparable ionic conductivity of matter is solved, by the way that stable SEI not only can be generated in one layer of fast-ionic conductor of Graphite Coating
Film, and ion-diffusibility can be enhanced, the oxidation-reduction potential of fast-ionic conductor is higher than graphite, can be to avoid pole under low temperature
Li dendrite caused by changing generates, and improves safety.
Detailed description of the invention
Fig. 1 is that the titanium phosphate lithium that the present invention obtains in embodiment 1 coats metallic nickel intercalated graphite composite material in difference
At a temperature of 0.2C discharge curve；
Fig. 2 is that the titanium phosphate lithium that the present invention obtains in embodiment 1 coats metallic nickel intercalated graphite composite material at -20 DEG C
Lower cyclic curve；
Fig. 3 is the titanium phosphate lithium coated graphite composite material of the invention obtained in example 4 0.2C at different temperatures
Discharge curve；
Fig. 4 is the 0.2C discharge voltage-appearance at different temperatures of metallic nickel intercalated graphite composite material obtained in comparative example 1
Measure curve；
Fig. 5 is graphite cathode material of the present invention in comparative example 3 0.2C discharge curve at different temperatures；
Fig. 6 is the cyclic curve at -20 DEG C of the graphite cathode material obtained in comparative example 3 of the invention；
The electric discharge open-circuit voltage of the graphite material in embodiment 1 and platform voltage are with temperature as can be seen from Figure 1
Variable quantity is very small, and the capacity retention ratio of system has 93.5% at -40 DEG C, and cryogenic property is very excellent.And it is recycled from Fig. 2 bent
Line can be seen that 200 multi-turn capacity retention rates are recycled at -20 DEG C is still maintained at 95% or so.
The electric discharge open-circuit voltage of the graphite material in embodiment 4 and platform voltage are at -30 DEG C or more as can be seen from Figure 3
As the variable quantity of temperature is very small, -40 DEG C of whens, decline, and cryogenic property is good.
As can be seen from Figure 4 with the reduction of temperature, the discharge curve decline of the graphite material in comparative example 1 is rapider,
Cryogenic property is slightly worse.
Battery performance lands vertically trend under low temperature as can be seen from Figure 5, and in -40C, capacity retention ratio is only 1.4%, explanation
Material has excessively poor cryogenic property, and can be seen that ten multi-turn capacity of recurring number is protected at -20C from Fig. 6 cyclic curve
Rate is stayed just to decline quickly.
Specific embodiment
The preparation process of positive plate: by positive electrode LiCoO2With PVDF, SP, KS-6 (LiCoO in mass ratio2: PVDF:
SP:KS-6=94.5:2.5:2:1 composition) dry powder 0.5h is mixed at a slow speed by double planetary mixer, then press solid-to-liquid ratio
The NMP of certain mass is added in 74%:26%, stirs 6h slurrying；By the slurry made by coating machine by 20mg cm-2Unit
Area quality is uniformly coated on the aluminium foil of 16 μ m-thicks, roll-in is carried out after drying, wherein LiCoO2System compacted density (concora crush pressure
The quality of next unit volume) it is 3.9g cm-3。
The preparation process of negative electrode tab: by the graphite material of preparation and CMC, SBR, SP (graphite in mass ratio: CMC:SBR:SP
=92.5:1.6:2.4:3.5 composition) dry powder 0.5h is mixed at a slow speed by double planetary mixer, then press solid-to-liquid ratio 52%:
48% is added the deionized water of certain mass, stirs 6h slurrying；By the slurry made by coating machine by it is corresponding anode for the first time
The mass area ratio that capacity has more 8% surplus is uniformly coated on the copper foil of 8 μ m-thicks, roll-in is carried out after drying, wherein graphite
Compacted density (concora crush compress after unit volume quality) be 1.55g cm-3。
The assembling of battery: cutting positive and negative anodes pole piece, welding electrode ear, and positive plate, negative electrode tab and diaphragm are passed through winding
Machine is wound in the volume heart of one fixed width and thickness, winds principle are as follows: must be isolated by diaphragm between positive electrode and negative electrode, width direction
Isolation film encases positive and negative anodes, and cathode encases anode；Then the volume heart is put by wrapping in the stamping forming aluminum plastic film of suitable dimension
Firmly, top margin and side are sealed on sealing machine, keep air sac belt flaring here；The 85 DEG C of bakings in vacuum oven of packaged battery
For 24 hours, it is taken after moisture is dried completely and carries out fluid injection into glove box, infiltration is pre- to seal；Then it is stood for 24 hours in 45 DEG C of high hot houses, it is quiet
The battery set, which is put into constant temperature and pressure formation cabinet, carries out initial charge, charges to 3.8V, generates to inside battery SEI film, secondary
Pumping sealing is carried out after the reaction was completed, and air sac belt is cut away, and completes the assembly of Soft Roll lithium ion full battery.
Embodiment 1
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.By the 30mL mixed in hydrochloric acid of graphite powder and 1mol/L, two are washed with deionized after 12h is stirred by ultrasonic
Then side is dried to obtain graphite oxide at 100 DEG C.Graphite oxide is added in 50mL ethanol solution, nickel acetate intercalation object is added
It with sodium borohydride reduction agent, is washed with ethanol solution to pH value 7 after ultrasonic disperse 6h, filtration product is heat-treated, tube furnace argon
300 DEG C are raised to 5 DEG C/min heating rate in nitrogen atmosphere, heat preservation 6h obtains metallic nickel intercalated graphite material；By metallic nickel intercalation
Graphite is added to 80mL ethanol solution, and lithium acetate, four fourth of metatitanic acid is added in the ratio that the molar ratio of lithium, titanium, phosphorus is 1.5:2:3.5
Ester, phosphoric acid, wherein the quality of butyl titanate is 5% weighing of graphite powder, carries out ingredient, obtains mixed liquor, hydrothermal temperature is
200 DEG C, the hydro-thermal time be for 24 hours, to hydrothermal product with ethanol washing twice, in tube furnace after dry 12h in 80 DEG C of baking ovens
In lead to argon gas sintering, heating rate is 5 DEG C/min, is warming up to 900 DEG C, 8h is kept the temperature, to generate titanium phosphate lithium cladding metallic nickel
Intercalated graphite composite material.
Embodiment 2
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.By the 30mL mixed in hydrochloric acid of graphite powder and 1mol/L, two are washed with deionized after 12h is stirred by ultrasonic
Then side is dried to obtain graphite oxide at 100 DEG C.Graphite oxide is added in 50mL ethanol solution, nickel acetate intercalation object is added
It with sodium borohydride reduction agent, is washed with ethanol solution to pH value 7 after ultrasonic disperse 6h, filtration product is heat-treated, tube furnace argon
300 DEG C are raised to 5 DEG C/min heating rate in nitrogen atmosphere, heat preservation 6h obtains metallic nickel intercalated graphite material；By metallic nickel intercalation
Graphite is added to 80mL ethanol solution, in lithium, titanium, phosphorus molar ratio be 1:2:3 ratio be added lithium acetate, butyl titanate,
Phosphoric acid, wherein the quality of butyl titanate is 2% weighing of graphite powder, carries out ingredient, obtains mixed liquor, hydrothermal temperature is 200
DEG C, the hydro-thermal time be for 24 hours, to hydrothermal product with ethanol washing twice, lead in tube furnace after dry 12h in 80 DEG C of baking ovens
Argon gas sintering, heating rate are 5 DEG C/min, are warming up to 900 DEG C, keep the temperature 8h, to generate titanium phosphate lithium cladding metallic nickel intercalation
Graphite composite material.The titanium phosphate lithium layer that the material coats compared with final product in embodiment 1 reduces, and -40 spend lower performance slightly
Almost.
Embodiment 3
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.By the 30mL mixed in hydrochloric acid of graphite powder and 1mol/L, two are washed with deionized after 12h is stirred by ultrasonic
Then side is dried to obtain graphite oxide at 100 DEG C.Graphite oxide is added in 50mL ethanol solution, nickel acetate intercalation object is added
It with sodium borohydride reduction agent, is washed with ethanol solution to pH value 7 after ultrasonic disperse 6h, filtration product is heat-treated, tube furnace argon
300 DEG C are raised to 5 DEG C/min heating rate in nitrogen atmosphere, heat preservation 6h obtains metallic nickel intercalated graphite material；By metallic nickel intercalation
Graphite is added to 80mL ethanol solution, and lithium acetate, four fourth of metatitanic acid is added in the ratio that the molar ratio of lithium, titanium, phosphorus is 1.5:2:4
Ester, phosphoric acid, wherein the quality of butyl titanate is 20% weighing of graphite powder, carries out ingredient, obtains mixed liquor, hydrothermal temperature is
200 DEG C, the hydro-thermal time be for 24 hours, to hydrothermal product with ethanol washing twice, in tube furnace after dry 12h in 80 DEG C of baking ovens
In lead to argon gas sintering, heating rate is 5 DEG C/min, is warming up to 900 DEG C, 8h is kept the temperature, to generate titanium phosphate lithium cladding metallic nickel
Intercalated graphite composite material.The titanium phosphate lithium layer that the material coats compared with final product in embodiment 1 is thicker, -30, -40 degree
Lower performance is slightly worse.
Embodiment 4
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.Graphite powder is added to 80mL ethanol solution, the ratio for being 1.5:2:3.5 by the molar ratio of lithium, titanium, phosphorus
Lithium acetate, butyl titanate, phosphoric acid is added in example, and wherein the quality of butyl titanate is 5% weighing of graphite powder, carries out ingredient,
Obtain mixed liquor, hydrothermal temperature is 200 DEG C, the hydro-thermal time be for 24 hours, to hydrothermal product with ethanol washing twice, in 80 DEG C of baking ovens
Lead to argon gas sintering after interior dry 12h in tube furnace, heating rate is 5 DEG C/min, is warming up to 900 DEG C, keeps the temperature 8h, thus raw
At titanium phosphate lithium coated graphite composite material.
Comparative example 1
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.By the 30mL mixed in hydrochloric acid of graphite powder and 1mol/L, two are washed with deionized after 12h is stirred by ultrasonic
Then side is dried to obtain graphite oxide at 100 DEG C.Graphite oxide is added in 50mL ethanol solution, nickel acetate intercalation object is added
It with sodium borohydride reduction agent, is washed with ethanol solution to pH value 7 after ultrasonic disperse 6h, filtration product is heat-treated, tube furnace argon
300 DEG C are raised to 5 DEG C/min heating rate in nitrogen atmosphere, heat preservation 6h obtains metallic nickel intercalated graphite material.
Comparative example 2
It weighs 10g natural graphite powder to be dissolved in the deionized water of 20mL, stir evenly, place in ball grinder, with 400r/
The revolving speed ball milling 12h of min, the good slurry of ball milling is granulated using spray dryer, and inlet air temperature is 220 DEG C, leaving air temp is
120℃；Graphite powder is made.By the 30mL mixed in hydrochloric acid of graphite powder and 1mol/L, two are washed with deionized after 12h is stirred by ultrasonic
Then side is dried to obtain graphite oxide at 100 DEG C.Graphite oxide is added in 50mL ethanol solution, nickel acetate intercalation object is added
It with sodium borohydride reduction agent, is washed with ethanol solution to pH value 7 after ultrasonic disperse 6h, filtration product is heat-treated, tube furnace argon
300 DEG C are raised to 5 DEG C/min heating rate in nitrogen atmosphere, heat preservation 6h obtains metallic nickel intercalated graphite material；By metallic nickel intercalation
Graphite is added to 80mL ethanol solution, and lithium acetate, four fourth of metatitanic acid is added in the ratio that the molar ratio of lithium, titanium, phosphorus is 1.5:2:3.5
Ester, phosphoric acid, wherein the quality of butyl titanate is 40% weighing of graphite powder, carries out ingredient, obtains mixed liquor, hydrothermal temperature is
200 DEG C, the hydro-thermal time be for 24 hours, to hydrothermal product with ethanol washing twice, in tube furnace after dry 12h in 80 DEG C of baking ovens
In lead to argon gas sintering, heating rate is 5 DEG C/min, is warming up to 900 DEG C, 8h is kept the temperature, to generate titanium phosphate lithium cladding metallic nickel
Intercalated graphite composite material.The titanium phosphate lithium layer that the material coats compared with final product in embodiment 1 is blocked up, with graphite ratio
Quite, capacity is very low.
Comparative example 3:
Processing any to natural graphite powder is not also done, and is used directly to do negative electrode material.
Claims (10)
1. a kind of low-temperature lithium ion battery graphite cathode material；It is characterized by: the low-temperature lithium ion battery graphite cathode material
Material includes the fast-ionic conductor of graphite and Graphite Coating；The oxidation-reduction potential of the fast-ionic conductor is higher than graphite.
2. a kind of low-temperature lithium ion battery graphite cathode material according to claim 1；It is characterized by: the low temperature lithium
Ion battery graphite cathode material is made of the fast-ionic conductor of intercalated graphite, graphite layers conductive material and Graphite Coating.
3. a kind of low-temperature lithium ion battery graphite cathode material according to claim 2；It is characterized by: the graphite linings
Between conductive material be transformed during the sintering process by intercalation object；The intercalation object be selected from aniline, pyrroles, pink salt, cobalt salt, molysite,
At least one of nickel salt, manganese salt；
The pink salt is selected from least one of the chlorate of tin, the acetate of tin, the sulfate of tin, the nitrate of tin；
The cobalt salt is selected from least one of the chlorate of cobalt, the acetate of cobalt, the sulfate of cobalt, the nitrate of cobalt；
The molysite is selected from least one of the chlorate of iron, the acetate of iron, the sulfate of iron, the nitrate of iron；
The nickel salt is selected from least one of the chlorate of nickel, the acetate of nickel, the sulfate of nickel, the nitrate of nickel；
The manganese salt is selected from least one of the chlorate of manganese, the acetate of manganese, the sulfate of manganese, the nitrate of manganese；
The fast-ionic conductor includes LiM2(PO4)3And/or with LiM2(PO4)3For a series of doped products of parent, the M choosing
From at least one of Zr, Sc, Ti, Ge；The element wherein adulterated be selected from Si, Al, La, Mg, Zn, Sn, Fe, Mn, Co, Ni, Cu,
W, at least one of Mo, V, Cr.
4. a kind of low-temperature lithium ion battery graphite cathode material according to claim 1；It is characterized by: the fast ion
Conductor is coated on graphite surface and forms the clad that a layer thickness is 1-10nm.
5. a kind of method for preparing the low-temperature lithium ion battery graphite cathode material as described in claim 1-4 any one；It is special
Sign is；Include the following steps:
Using intercalated graphite as raw material；Lithium source, the source M, doped chemical, phosphorus source will be added after intercalated graphite wiring solution-forming；Using hydro-thermal
Method or solvent-thermal method coat one layer of fast-ionic conductor in intercalated graphite；Then washed, dry, sintering, obtains the low temperature
Graphite negative material of lithium ion battery；Be added lithium source, the source M, doped chemical, after phosphorus source, lithium in system, M, phosphorus molar ratio be 1-
1.5:2:3-4；The source M provides at least one of Zr, Sc, Ti, Ge of non-zero valence element；The doped chemical be selected from Si,
At least one of Al, La, Mg, Zn, Sn, Fe, Mn, Co, Ni, Cu, W, Mo, V, Cr.
6. a kind of preparation method of low-temperature lithium ion battery graphite cathode material according to claim 5, it is characterised in that:
When the source M is titanium source；The titanium source is butyl titanate or isopropyl titanate.
Phosphorus source is selected from least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid；
The lithium source is selected from least one of lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate.
7. a kind of preparation method of low-temperature lithium ion battery graphite cathode material according to claim 5, it is characterised in that:
After lithium source, the source M, doped chemical, phosphorus source is added after intercalated graphite wiring solution-forming, intercalated graphite composite material sol is obtained
Liquid；In the intercalated graphite composite material solution, lithium, M, phosphorus molar ratio be 1-1.5:2:3-4；In the M and intercalated graphite
The mass ratio of graphite is 1-20:100；Doped chemical and the molar ratio of M are 0-5:10；
Hydro-thermal method or solvent-thermal method when coating one layer of fast-ionic conductor in intercalated graphite, controlled at 160~230 DEG C, when
Between be 6~48h；
For hydro-thermal method when coating one layer of fast-ionic conductor in intercalated graphite, solvent is deionized water or dehydrated alcohol, ethylene glycol, third
The mixture that at least one of ketone is formed with water；
For solvent-thermal method when coating one layer of fast-ionic conductor in intercalated graphite, solvent is in dehydrated alcohol, ethylene glycol, acetone
It is at least one.
8. a kind of preparation method of low-temperature lithium ion battery graphite cathode material according to claim 5, it is characterised in that:
When the sintering, it is sintered using protective atmosphere；The protective atmosphere is in argon atmosphere, nitrogen atmosphere, vacuum atmosphere
One kind；It is 1~10 DEG C/min that heating rate is controlled when sintering, and sintering temperature is 600~900 DEG C, guarantor at a sintering temperature
The warm time be 4~for 24 hours.
9. a kind of preparation method of low-temperature lithium ion battery graphite cathode material according to claim 5, it is characterised in that；
The intercalated graphite is prepared by following step:
Step 1
Graphite powder is added to progress wet process stirring ball-milling in ball mill, mixed solution is spray-dried；
Step 2
After graphite powder obtained by step 1 is mixed with concentrated acid, graphite oxide is obtained after ultrasonic agitation, centrifugal drying；
Step 3
Graphite oxide wiring solution-forming obtained in step 2, is added intercalation object and reducing agent, after ultrasonic disperse that solution is washed
Filter, is heat-treated filtration product to obtain intercalated graphite material.
10. a kind of preparation method of low-temperature lithium ion battery graphite cathode material according to claim 5, feature exist
In:
Ball milling solvent described in step 1 is selected as deionized water or dehydrated alcohol；After solvent is added, slurry, stone in slurry are constituted
Black mass fraction is 30~70%；
Graphite powder described in step 1 is one kind of natural graphite, artificial graphite or carbonaceous mesophase spherules；Its partial size is 30-100
Micron；
Ball-milling Time 4-24h described in step 1, the revolving speed of ball milling are 200-400r/min；It is warm using being entered the wind when spray dryer
Degree is 200-300 DEG C, leaving air temp is 100-150 DEG C；The granularity that graphite is made is 1-20um；
Concentrated acid described in step 2 is one kind of hydrochloric acid or nitric acid, and concentrated acid concentration is 0.5-3mol/L；3-24h is stirred by ultrasonic；
Drying temperature is at 60-200 DEG C；
Intercalation object described in step 3 be aniline, pyrroles or metallic tin, cobalt, iron, the chlorate of nickel and manganese, acetate, sulfate,
Nitrate；Intercalation object is converted to graphite layers conductive material during the sintering process；
Reducing agent described in step 3 is hydrazine hydrate, D-araboascorbic acid sodium, sodium sulfite, azanol or sodium borohydride；
Ultrasonic disperse 1-12h described in step 3；Solution is washed to pH value 6-8；Tube furnace heating rate is 1-10 DEG C/min, temperature
Degree is 180-600 DEG C, time 2-12h；Atmosphere is selected from argon atmosphere, nitrogen atmosphere, argon nitrogen atmosphere, carbon dioxide atmosphere, hydrogen
At least one of atmosphere, nitrogen dioxide atmosphere.
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Cited By (11)
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|---|---|---|---|---|
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379062C (en) * | 2002-06-21 | 2008-04-02 | 优米科尔公司 | Carbon-coated Li-containing powders and process for production thereof |
| CN101214952A (en) * | 2007-12-31 | 2008-07-09 | 平顶山工学院 | Modified method of natural graphite material for lithium ion battery |
| CN102340006A (en) * | 2011-09-30 | 2012-02-01 | 湖南大学 | Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments |
| CN102646818A (en) * | 2012-04-28 | 2012-08-22 | 中南大学 | Preparation method for composite cathode material of lithium ion battery |
| US20120258362A1 (en) * | 2011-04-08 | 2012-10-11 | Samsung Electronics Co. Ltd. | Electrode active material, method of preparing electrode active material, electrode including electrode active material, and lithium secondary battery including electrode |
| CN103296277A (en) * | 2012-03-01 | 2013-09-11 | 复旦大学 | Graphite intercalation compound lithium-ion battery negative electrode material, as well as preparation method and application thereof |
| US20130260246A1 (en) * | 2012-04-02 | 2013-10-03 | Guorong Chen | Lithium-ion cell having a high energy density and high power density |
| CN103904305A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery |
| CN103904304A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery |
| WO2015132845A1 (en) * | 2014-03-03 | 2015-09-11 | 株式会社日立製作所 | All-solid-state battery |
| CN106876707A (en) * | 2017-04-05 | 2017-06-20 | 宁波力赛康新材料科技有限公司 | A kind of solid lithium battery |
| CN107743645A (en) * | 2015-04-23 | 2018-02-27 | 威廉马歇莱思大学 | Carbon nano pipe array as the vertical alignment of electrode |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
| CN107946576A (en) * | 2017-11-21 | 2018-04-20 | 中航锂电（洛阳）有限公司 | A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery |
-
2018
- 2018-06-22 CN CN201810647061.5A patent/CN108987687B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379062C (en) * | 2002-06-21 | 2008-04-02 | 优米科尔公司 | Carbon-coated Li-containing powders and process for production thereof |
| CN101214952A (en) * | 2007-12-31 | 2008-07-09 | 平顶山工学院 | Modified method of natural graphite material for lithium ion battery |
| US20120258362A1 (en) * | 2011-04-08 | 2012-10-11 | Samsung Electronics Co. Ltd. | Electrode active material, method of preparing electrode active material, electrode including electrode active material, and lithium secondary battery including electrode |
| CN102340006A (en) * | 2011-09-30 | 2012-02-01 | 湖南大学 | Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments |
| CN103296277A (en) * | 2012-03-01 | 2013-09-11 | 复旦大学 | Graphite intercalation compound lithium-ion battery negative electrode material, as well as preparation method and application thereof |
| US20130260246A1 (en) * | 2012-04-02 | 2013-10-03 | Guorong Chen | Lithium-ion cell having a high energy density and high power density |
| CN102646818A (en) * | 2012-04-28 | 2012-08-22 | 中南大学 | Preparation method for composite cathode material of lithium ion battery |
| CN103904305A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery |
| CN103904304A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery |
| WO2015132845A1 (en) * | 2014-03-03 | 2015-09-11 | 株式会社日立製作所 | All-solid-state battery |
| CN107743645A (en) * | 2015-04-23 | 2018-02-27 | 威廉马歇莱思大学 | Carbon nano pipe array as the vertical alignment of electrode |
| CN106876707A (en) * | 2017-04-05 | 2017-06-20 | 宁波力赛康新材料科技有限公司 | A kind of solid lithium battery |
| CN107946576A (en) * | 2017-11-21 | 2018-04-20 | 中航锂电（洛阳）有限公司 | A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
Non-Patent Citations (1)
| Title |
|---|
| YONG YAN, LIUBIN BEN, YUANJIE ZHAN, XUEJIE HUANG: "Nano-Sn embedded in expanded graphite as anode for lithium ion batteries with improved low temperature electrochemical performance", 《ELECTROCHIMICA ACTA》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817983A (en) * | 2019-01-03 | 2019-05-28 | 江西星盈科技有限公司 | Lithium ion battery and its negative electrode tab and negative electrode material and preparation process |
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| CN111613771A (en) * | 2020-06-29 | 2020-09-01 | 蜂巢能源科技有限公司 | Battery cathode and preparation method and application thereof |
| CN113889595A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of solid electrolyte coated graphite composite material |
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| CN112174218A (en) * | 2020-09-30 | 2021-01-05 | 厦门厦钨新能源材料股份有限公司 | Lithium cobaltate and preparation method and application thereof |
| CN112174218B (en) * | 2020-09-30 | 2022-05-20 | 厦门厦钨新能源材料股份有限公司 | Lithium cobaltate and preparation method and application thereof |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
| CN113363444A (en) * | 2021-06-15 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Nano lithium titanate-coated modified graphite negative electrode material, and preparation method and application thereof |
| CN113363444B (en) * | 2021-06-15 | 2022-07-15 | 广东凯金新能源科技股份有限公司 | Nano lithium titanate-coated modified graphite negative electrode material, and preparation method and application thereof |
| CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
| CN114628659A (en) * | 2022-04-18 | 2022-06-14 | 晖阳(贵州)新能源材料有限公司 | Graphite cathode composite material for power battery and preparation method thereof |
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