CN108666551A - A kind of graphene/LiTi2(PO4)3Lithium cell cathode material and preparation method - Google Patents
A kind of graphene/LiTi2(PO4)3Lithium cell cathode material and preparation method Download PDFInfo
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Abstract
The invention belongs to technical fields prepared by lithium battery, and in particular to a kind of graphene/LiTi2(PO4)3Lithium cell cathode material and preparation method.A kind of graphene/LiTi of the present invention2(PO4)3Lithium cell cathode material and preparation method replace traditional high temperature process heat method to obtain the macropore LiTi of nanoscale due to the sol-gal process assisted using polyvinyl alcohol2(PO4)3, material granule is smaller, and conductivity increases after the coated graphite alkene layer of surface, LiTi2(PO4)3The performance for showing good large current charge, specific capacity still keeps 85% or more under the charge-discharge magnification of 20C.Clad can allow lithium ion to pass through, to effectively prevent the generation of the side reaction of electrode material and water so that LiTi2(PO4)3Cycle performance be greatly improved, while there is excellent chemical property and stability.
Description
Technical field
The invention belongs to technical fields prepared by lithium battery, and in particular to a kind of graphene/LiTi2(PO4)3Lithium battery is negative
Pole material and preparation method.
Background technology
Lithium ion inlaid scheme was used from 1990（Carbon and cobalt acid lithium）With the lithium ion battery quotient of organic electrolyte
Since product, the advantages of with its high-energy-density, compact battery market has been captured rapidly, and be widely used in mobile phone, notebook
The various communication devices such as computer, video camera.However, although organic series lithium ion battery has many advantages, what is used has
Solvent is not only toxic but also inflammable, if using inappropriate, can bring many safety issues.In addition production cost is also because of nothing
Water operating environment and greatly improve, these deficiencies greatly limit its application in large-scale energy-storage battery.In order to solve lithium from
On the one hand the problem of sub- battery security, can select the electrode material of high security, or use additives for overcharge protection agent, can also
Noninflammability electrolyte is added；The method of another relative efficiency is to use aqueous solution electrolysis liquid, because aqueous solution electrolysis liquor ratio has
The ionic conductivity of machine electrolyte improves several orders of magnitude, and the specific power of battery is expected to be improved.Moreover it is possible to avoid adopting
Harsh assembling condition, greatly reduces cost necessary to organic electrolyte.Since aquo-lithium ion battery is with acyclic
The advantages that border pollutes, is cheap, power is high and security performance is high, becomes the accumulator of new generation with development and application potentiality
Part.It also will be as one of the hot spot of electrochemical energy storage area research to the research of aquo-lithium ion battery and its associated materials.
Aquo-lithium ion battery has the advantages that cheap, non-environmental-pollution, security performance is high, high power, this electricity
Pond is expected in the future for energy storages, intelligent grid peak valley tune lotus and the short distance electric bus such as wind-force, solar power generation etc..
1994, Dahn seminar reported a kind of lithium ion battery with aqueous electrolyte for the first time in U.S.'s Science magazines, bore
Pole use VO2, anode use LiMn2O4, electrolyte solution be subalkaline Li2SO4 solution, average working voltage 1.5V,
The energy density of this battery is more than lead-acid battery close to 40Wh/kg in practical application（30Wh/kg）, with Ni-Cd battery phases
When, but cycle performance is very poor, keeps this kind of battery life shorter.In order to improve cycle performance, raising cell charging times are past
Many researchs concentrate on studying on suitable electrode material, to improve cycle performance.Fudan University by it is theoretical and it is experimentally confirmed that
In the presence of water and oxygen, it is that aquo-lithium ion battery capacity is caused to decline that the electrode material as battery cathode, which can be oxidized by oxygen,
The main reason for subtracting.
Chinese invention patent application number 201510184862.9 discloses a kind of water system lithium（Sodium）Ion battery mixing cathode
Material.Mix negative material by：Ion embedded type compound, conductive material, energy reversible storage alkali or alkaline earth metal ion
Organic compound or high molecular polymer three types material mixed in certain mass ratio；Its hybrid mode includes original
Position growth and the direct mechanical mixture of each component part.The water system lithium assembled as cathode using this mixed electrode material（Sodium）Ion
Battery has the characteristics that long cycle life, high-power, high security, low cost and non-environmental-pollution, is particularly well suited as
The power battery of neighborhood electric vehicle and the energy-storage battery of intelligent grid.
What Chinese invention patent application number 201410532824.3 disclosed a kind of long-life high-energy density can charge and discharge water
It is ion battery.The present invention can charge and discharge water system ion battery, including cathode film, negative electrode film, diaphragm and electrolyte, feature exist
In：Electrolyte uses the alkali metal ion aqueous solution containing buffer.The cation of the buffer be lithium ion, sodium ion,
One or more of potassium ion, hydrogen ion, ammonium root；The anion of the buffer is acetate, phosphate radical, carbonate, lemon
One or more of lemon acid group, formate.Feature of present invention is that water system ion battery electrolyte contains buffer, is filled in battery
Buffer is capable of the pH value of stabilising system in discharge process, inhibits analysis oxygen and liberation of hydrogen side reaction, to improve battery energy density
And cycle life.The water system of the present invention can charge and discharge battery have the characteristics that electrochemical energy height, good cycle, environmentally protective,
Has broad mass market foreground.
It is compound that Chinese invention patent application number 201710984589.7 discloses a kind of hard carbon/graphene for lithium battery
The preparation method of negative material.After organic polymer is carried out stabilization processes by this method, it has been mixed in sheet graphene
In solvent, temperature reaction after supersound process obtains the composite precursor of hard carbon/graphene.Then by presoma and nanosphere
Shape metal powder mixes, and high temperature thermal decomposition is carried out under gas shield, spherical hard carbon is formed and is coated on nanometer spherical metal powder
Surface, and be clipped between lamellar graphite alkene to get hard carbon/graphene composite negative pole.Compared with conventional method, the present invention
The electrode capacity of hard carbon/graphene composite negative pole of preparation is big, and the lithium battery assembled, stability is preferable, cycle
Better performances overcome general anode material reversible specific capacity and lose larger defect, and whole preparation process is easy to control, outside product
It sees and performance is stablized, sexual valence is relatively high.
Chinese invention patent application number 201611148215.3 discloses a kind of graphene lithium battery comprising shell and electricity
Core；The enclosure interior is equipped with cavity, and the wall portion of the shell is convexly equipped with several bodies to the cavity, and described body has shape
Change portion；The anode ear and negative electrode lug of mutually insulated are equipped on the shell；The battery core is placed in the cavity, and at least
One described body is in contact so that the deformations of described body deform upon, and the battery core has positive electrode and negative electrode,
The positive electrode is connect with the anode ear, and the negative electrode is connect with the negative electrode lug；The positive electrode has electrode film,
Grapheme material is set on the electrode film.Using the above scheme, the present invention proposes setting graphene material on electrode film
The deformations of the graphene lithium battery technology of material, and by optimization design shell, battery core body when mounted deform upon, and make
It obtains battery core to be more easily installed, and fixed effect is more preferable.
The seminar of Chinese Academy of Sciences CAS Institute of Physics Chen Li spring academicians reported anode in 2006 and uses LiMn2O4, cathode use
TiP2O7And LiTi2(PO4)3, electrolyte be LiNO3The aquo-lithium ion battery of solution.Positive electrode LiMn is thought in the research2O4
There is stability, but negative material LiTi in aqueous solution2(PO4)3The decomposition of crystal structure can occur and generate novel substance and to hold
Amount declines, and results in entire battery capacity decaying.
Invention content
For water system cathode of lithium battery capacity fade problem, the present invention proposes a kind of graphene/LiTi2(PO4)3Lithium battery
Negative material and preparation method.
To solve the above problems, the present invention uses following technical scheme：
A kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 8~12 DEG C of min-1Heating rate is heated to 900~950 DEG C, keeps the temperature 8~12h, obtains having large aperture
LiTi2(PO4)3Compound；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 500 ~ 800 DEG C, is passed through carbon-source gas, increases temperature to 900~1200 DEG C, carbon-source gas cracks and starts hydrogenating
Metallic film surface generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, be cooled to
After room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Negative material.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein a steps
Described in Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 6~10:0.5~1.5:0.5~1.5.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein a steps
Described in it is dry at 80 DEG C it is dry for 24 hours.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein a steps
Described in 10 DEG C of min-1Heating rate is heated to 930 DEG C, keeps the temperature 10h.
NASICON structures are electronegative three-dimensional framework, structural formula Ti2P3O12, it is by PO4Tetrahedron and TiO6Octahedral
Body is connected, each TiO6Octahedra and 6 PO4Tetrahedron is connected, Li+It is migrated in the three-dimensional channel of crystal structure.
LiTi2(PO4)3Belong to NASICON type superionic conductors materials, there are two types of different Li+Position (M1 and M2), M1 is completely filled,
And M2 is vacancy.In discharge process, there are two Li+Embedded LiTi2(PO4)3Middle formation Li3Ti2(PO4)3, the process of charging
Two Li+From Li3Ti2(PO4)3Middle abjection forms LiTi2(PO4)3。LiTi2(PO4)3There is the theory of 138.3mAh/g is initial to hold
Amount, intercalation potential is in 2.5 V or so, and its suction puts lithium process with flat electrochemical reaction platform, can provide stabilization
Operating voltage, can be with the positive electrode LiMn that studies extensively now2O4, LiCoO2Etc. aqueous lithium ion battery is formed, to reduce
Battery cost.At present about LiTi2(PO4)3High temperature solid-state method is mostly used to be made.Further, above-mentioned a kind of graphene/LiTi2
(PO4)3The preparation method of lithium cell cathode material, the wherein LiTi of large aperture described in a steps2(PO4)3The grain size of compound is
100~300nm, aperture are 10~30 μm.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein b step
Described in metal hydride film be Pd, V, Ti, Al, Nb, Zr, Y, Er, La at least one of hydride films.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein b step
Described in metal hydride film thickness be 0.2~0.8 μm.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein step c
Described in carbon-source gas be at least one of methane, acetylene or propylene.
Further, above-mentioned a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, wherein step c
Described in diluted acid be at least one of dilute hydrochloric acid of a concentration of 1~3mol/L, dilute sulfuric acid, dust technology.
The present invention also provides a kind of graphene/LiTi that a kind of above-mentioned preparation method is prepared2(PO4)3Cathode of lithium battery
The macropore LiTi of nanoscale has been prepared in material, the sol-gel method assisted using polyvinyl alcohol2(PO4)3, by macropore
LiTi2(PO4)3Metal hydride film is plated, starts plasmasphere and heating power supply, is preheated to 500 ~ 800 DEG C, is passed through carbon-source gas,
Graphene starts to grow, and after the completion of waiting for graphene growth, closes heating power supply, plasma electrical source is closed, at cathode cooling
Reason after being cooled to room temperature, is taken out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode
Material.
A kind of graphene/LiTi of the present invention2(PO4)3Lithium cell cathode material and preparation method, due to utilizing polyvinyl alcohol
The sol-gel method of auxiliary replaces traditional high temperature process heat method to have obtained the macropore LiTi of nanoscale2(PO4)3,
Material granule is smaller, and conductivity increases after the coated graphite alkene layer of surface, LiTi2(PO4)3Good high current is shown to fill
The performance of electricity, specific capacity still keeps 85% or more under the charge-discharge magnification of 20C.Clad can allow lithium ion to pass through, to have
Effect prevents the generation of the side reaction of electrode material and water so that LiTi2(PO4)3Cycle performance be greatly improved,
There is excellent chemical property and stability simultaneously.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 8 DEG C of min-1Heating rate is heated to 900 DEG C, keeps the temperature 8h, obtains with grain size being 100nm, aperture is 20 μ
The large aperture LiTi of m2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 6:0.5:1；It is described dry
Dry is to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Pd；The thickness of the metal hydride film is 0.4 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 500 DEG C, is passed through carbon-source gas, increases temperature to 1000 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, after being cooled to room temperature, take
Go out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Negative material；The carbon-source gas
For methane；The diluted acid is the dilute hydrochloric acid of a concentration of 2mol/L.
By 1 gained graphene coated LiTi of embodiment2(PO4)3Negative material respectively with conductive agent acetylene black, binder
PVDF is mixed according to mass ratio 80: 10: 10, uses NMP（1-Methyl-2-Pyrrolidone）This mixture is modulated into slurry, uniformly
Coated on copper foil, 100 DEG C are dried in vacuo 24 hours, obtained experimental cell pole piece.It is to electrode with lithium piece, electrolyte is
The LiPF of 1mol/L6Solution, solvent EC（Ethyl carbonate ester）+DMC（Dimethyl carbonate）（Volume ratio 1: 1）, diaphragm is
Celgard2400 films are assembled into CR2025 type button cells in the glove box full of argon gas atmosphere.
By 1 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
118mAh/g is recycled 400 times, specific discharge capacity 106mAh/g.
Embodiment 2
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 10 DEG C of min-1Heating rate is heated to 920 DEG C, keeps the temperature 10h, obtains with grain size being 200nm, aperture is
20 μm of large aperture LiTi2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 6:0.7: 1.5；
The drying is to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Ti；The thickness of the metal hydride film is 0.4 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 600 DEG C, is passed through carbon-source gas, increases temperature to 1100 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode material
Material；The carbon-source gas is acetylene；The diluted acid is the dust technology of a concentration of 2mol/L.
By 2 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
114mAh/g is recycled 400 times, specific discharge capacity 101mAh/g.
Embodiment 3
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 11 DEG C of min-1Heating rate is heated to 930 DEG C, keeps the temperature 9h, obtains with grain size being 200nm, aperture 20
μm large aperture LiTi2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 10:0.5:1；It is described
It dries to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is La；The thickness of the metal hydride film is 0.4 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 700 DEG C, is passed through carbon-source gas, increases temperature to 1000 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode material
Material；The carbon-source gas is propylene；The diluted acid is the dilute sulfuric acid of a concentration of 3mol/L.
By 3 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
115mAh/g is recycled 400 times, specific discharge capacity 108mAh/g.
Embodiment 4
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 12 DEG C of min-1Heating rate is heated to 900 DEG C, keeps the temperature 8h, obtains with grain size being 100nm, aperture 20
μm large aperture LiTi2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 9:0.5: 1.5；Institute
It states and dries to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Al；The thickness of the metal hydride film is 0.5 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 600 DEG C, is passed through carbon-source gas, increases temperature to 1100 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode material
Material；The carbon-source gas is acetylene；The diluted acid is the dilute hydrochloric acid of a concentration of 2mol/L.
By 4 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
110mAh/g is recycled 400 times, specific discharge capacity 97mAh/g.
Embodiment 5
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 9 DEG C of min-1Heating rate is heated to 920 DEG C, keeps the temperature 10h, obtains with grain size being 250nm, aperture 20
μm large aperture LiTi2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 7:1: 1；It is described dry
Dry is to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Nb；The thickness of the metal hydride film is 0.7 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 600 DEG C, is passed through carbon-source gas, increases temperature to 1000 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode material
Material；The carbon-source gas is methane；The diluted acid is the dilute sulfuric acid of a concentration of 2mol/L.
By 5 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
112mAh/g is recycled 400 times, specific discharge capacity 100mAh/g.
Embodiment 6
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 10 DEG C of min-1Heating rate is heated to 930 DEG C, keeps the temperature 10h, obtains with grain size being 200nm, aperture is
20 μm of large aperture LiTi2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 7:1:0.8；It is described
It dries to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Y；The thickness of the metal hydride film is 0.6 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 600 DEG C, is passed through carbon-source gas, increases temperature to 1000 DEG C, carbon-source gas cracks and starts in metal hydride film table
Face generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Cathode material
Material；The carbon-source gas is propylene；The diluted acid is the dust technology of a concentration of 3mol/L.
By 6 gained graphene coated LiTi of embodiment2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
109mAh/g is recycled 400 times, specific discharge capacity 97mAh/g.
Comparative example 1
LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 8 DEG C of min-1Heating rate is heated to 900 DEG C, keeps the temperature 8h, obtains with grain size being 100nm, aperture is 20 μ
The large aperture LiTi of m2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 6:0.5:1；It is described dry
Dry is to be dried for 24 hours at 80 DEG C；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；The hydrogen
Change the hydride films that metal film is Pd；The thickness of the metal hydride film is 0.4 μm；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 500 DEG C, increases temperature to 1000 DEG C, closes heating power supply, close plasma electrical source, handles cathode cooling,
After being cooled to room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain LiTi2(PO4)3Negative material；The carbon source
Gas is methane；The diluted acid is the dilute hydrochloric acid of a concentration of 2mol/L.
By 1 gained LiTi of comparative example2(PO4)3Negative material presses quality with conductive black, activated carbon, binder (PTFE)
Than being 7:1:1:1 is dissolved in ethanol in proper amount solution, after mixing, is rolled into the film that thickness is 0 .04mm with roll squeezer, assigns
It gives on stainless (steel) wire collector, negative electrode plate is made.With LiMn2O4 (LMO) be anode, with conductive black (Super P),
Binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, prepares positive plate with in collector after mixing.With
1mol/L lithium sulfate aqueous solutions are electrolyte, and cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
94mAh/g is recycled 400 times, specific discharge capacity 71mAh/g.
Comparative example 2
Graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, includes the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 8 DEG C of min-1Heating rate is heated to 900 DEG C, keeps the temperature 8h, obtains with grain size being 100nm, aperture is 20 μ
The large aperture LiTi of m2(PO4)3Compound；The Li2CO3、NH4H2PO4、TiO2The molar ratio of three is 6:0.5:1；It is described dry
Dry is to be dried for 24 hours at 80 DEG C；
B, start plasmasphere and heating power supply, the large aperture LiTi that a steps are obtained2(PO4)3Compound is preheated to 500 DEG C,
It is passed through carbon-source gas, increases temperature to 1000 DEG C, carbon-source gas cracks and starts in LiTi2(PO4)3Composite surface generates stone
Black alkene after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, handles cathode cooling, be cooled to room
Wen Hou takes out, and washing is dried to obtain graphene coated LiTi2(PO4)3Negative material；The carbon-source gas is methane；It is described dilute
Acid is the dilute hydrochloric acid of a concentration of 2mol/L.
By 2 gained graphene coated LiTi of comparative example2(PO4)3Negative material and conductive black, activated carbon, binder (
PTFE it is) 7 in mass ratio:1:1:1 is dissolved in ethanol in proper amount solution, and after mixing, it is 0 to be rolled into thickness with roll squeezer
.04mm film assigns on stainless (steel) wire collector, and negative electrode plate is made.It is anode with LiMn2O4 (LMO), with conductive charcoal
Black (Super P), binder (PTFE) in mass ratio 8:1:1 is dissolved in ethanol solution, after mixing with in afflux
Body prepares positive plate.Using 1mol/L lithium sulfates aqueous solution as electrolyte, cellulose acetate film is that diaphragm assembles experimental cell.
Charge-discharge performance test is carried out to the battery：At 80 DEG C, discharge specific volume for the first time under 20C charge-discharge magnifications
96mAh/g is recycled 400 times, specific discharge capacity 78mAh/g.
Claims (10)
1. a kind of graphene/LiTi2(PO4)3The preparation method of lithium cell cathode material, which is characterized in that include the following steps：
A, first PVA is dissolved in deionized water, Li is then added2CO3、NH4H2PO4、TiO2, fully dissolving is stirred, then 80
Form is stirred in DEG C stirring in water bath device into solid, it is dry, presoma is obtained after grinding, presoma is put into tube furnace, in Ar gas
Under atmosphere protection, with 8~12 DEG C of min-1Heating rate is heated to 900~950 DEG C, keeps the temperature 8~12h, obtains having large aperture
LiTi2(PO4)3Compound；
B, the LiTi with large aperture that a steps are prepared2(PO4)3Composite surface plates metal hydride film；
C, start plasmasphere and heating power supply, the surface that b step obtains is coated with to the LiTi of metal hydride film2(PO4)3It is compound
Object is preheated to 500 ~ 800 DEG C, is passed through carbon-source gas, increases temperature to 900~1200 DEG C, carbon-source gas cracks and starts hydrogenating
Metallic film surface generates graphene, after the completion of waiting for graphene growth, closes heating power supply, closes plasma electrical source, be cooled to
After room temperature, take out using diluted acid dipping removal metal, washing is dried to obtain graphene coated LiTi2(PO4)3Negative material.
2. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In Li described in a steps2CO3、NH4H2PO4、TiO2The molar ratio of three is 6~10:0.5~1.5:0.5~1.5.
3. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In it is to be dried for 24 hours at 80 DEG C to be dried described in a steps.
4. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In with 10 DEG C of min described in a steps-1Heating rate is heated to 930 DEG C, keeps the temperature 10h.
5. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In the LiTi of large aperture described in a steps2(PO4)3The grain size of compound is 100~300nm, and aperture is 10~30 μm.
6. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In metal hydride film described in b step is at least one of the hydride films of Pd, V, Ti, Al, Nb, Zr, Y, Er, La.
7. a kind of graphene/LiTi according to claim 1 or 62(PO4)3The preparation method of lithium cell cathode material, it is special
Sign is that the thickness of metal hydride film described in b step is 0.2~0.8 μm.
8. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In carbon-source gas described in step c is at least one of methane, acetylene or propylene.
9. a kind of graphene/LiTi according to claim 12(PO4)3The preparation method of lithium cell cathode material, feature exist
In diluted acid described in step c is at least one of dilute hydrochloric acid, dilute sulfuric acid, dust technology of a concentration of 1~3mol/L.
10. a kind of graphene/LiTi being prepared according to any one of claim 1~9 preparation method2(PO4)3Lithium electricity
Pond negative material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935800A (en) * | 2018-11-13 | 2019-06-25 | 五邑大学 | A kind of lithium ion battery LiTi2(PO4)3/C/Ti3SiC2The preparation method of composite negative pole material |
| CN111477863A (en) * | 2020-05-15 | 2020-07-31 | 宁波锋成纳米科技有限公司 | Graphene/lithium titanium phosphate composite material, preparation method thereof and lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935800A (en) * | 2018-11-13 | 2019-06-25 | 五邑大学 | A kind of lithium ion battery LiTi2(PO4)3/C/Ti3SiC2The preparation method of composite negative pole material |
| CN111477863A (en) * | 2020-05-15 | 2020-07-31 | 宁波锋成纳米科技有限公司 | Graphene/lithium titanium phosphate composite material, preparation method thereof and lithium ion battery |
| CN111477863B (en) * | 2020-05-15 | 2021-09-03 | 宁波锋成纳米科技有限公司 | Graphene/lithium titanium phosphate composite material, preparation method thereof and lithium ion battery |
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