CN102544468B - Mesoporous lithium titanate lithium ion battery negative material of carbon cladding and preparation method thereof - Google Patents
Mesoporous lithium titanate lithium ion battery negative material of carbon cladding and preparation method thereof Download PDFInfo
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Abstract
The invention discloses mesoporous lithium titanate lithium ion battery negative material of a kind of carbon cladding and preparation method thereof.This material, by the nanocrystalline particle agglomeration being self-assembly of a diameter of 0.1～10 μm of 5～150nm, has meso-hole structure, and average pore size is 2～6nm, and carbon content is 0.5～5%.This lithium titanate sample can be as lithium ion battery negative material.
Description
Technical field
The present invention relates to the mesoporous lithium titanate lithium ion battery negative material that a kind of carbon in field of lithium ion battery is coated with
And preparation method thereof.
Background technology
Along with global resources aggravation in short supply and the continuous deterioration of environment, the exploitation of green renewable new forms of energy gradually obtains people
Attention, cleaning energy storage device is by the concern energetically of countries in the world.Lithium ion battery has high voltage, high power capacity, volume
Little, light weight, memoryless function, have extended cycle life, the advantage such as security performance is good, pollute little, become current portable electronic and produce
The first choice of the rechargeable formula power supply of product, and have broad application prospects in the field such as electric automobile, space technology, it is mesh
Front various countries endeavour the energy storage device of exploitation.Although the graphite-like Carbon anode being widely used at present has with low cost, reversible embedding de-
Lithium functional, but the volume energy density of traditional graphite cathode material is relatively low, and irreversible capacity loss is relatively big, restriction
The application of high energy density cells, therefore seek to have that safety is good, reliability is high, the advantage such as long-life and high power new
Type lithium ion battery negative material is constantly subjected to the attention of scientific research personnel, is also the crucial technical problem needing to break through.
Lithium titanate is one of a new generation's lithium ion battery most promising negative pole candidate material, and its voltage platform is left at 1.5V
The right side, Theoretical Mass specific capacity is 175mAh g-1, the most this material has the advantage that (1) will not in charge and discharge process
Recurring structure changes, and is described as " zero strain material "；(2) relative to Li+The discharge voltage of/Li is higher, does not occurs with electrolyte
Reacting and be difficult to cause lithium metal to separate out, safety is secure；(3) lithium ion diffusion coefficient (2 × 10-8cm2/ s) compare Carbon anode
High an order of magnitude；(4) coulombic efficiency height, advantages of nontoxic raw materials, inexpensive, is suitable for environmental protection and large-scale development；(5) chemical stability
Well, prepare simply, be that the most promising lithium ion battery of one bears level material, it is contemplated that can accomplish something in terms of electrokinetic cell.
But, the electric conductivity of this material own is very poor, causes high power charging-discharging capacity the lowest, limits its Commercialization application.People
It is devoted to improve the electric conductivity research of this material, as being devoted to fine particle size or even nano level tool in preparation method always
There is the Li of meso-hole structure4Ti5O12Study on the synthesis, to shortening the migration path of lithium ion, improves high rate performance；From coating technology
Start with as carbon coated improves electric conductivity；Adulterate other metallic elements or by the Ti in lithium titanate4+Partial reduction becomes Ti3+, improve electricity
Conductance is to improve high rate performance etc..These methods, while to Li4Ti5O12High rate performance make moderate progress, but its performance still can not
Meet actual demand.The invention provides a kind of mesoporous lithium titanate anode material with high-rate charge-discharge capability and preparation thereof
Method, this material has the high-rate charge-discharge capability of excellence, and its preparation method is simple, controlled simultaneously, be prone to large-scale production.
Summary of the invention
It is an object of the invention to provide mesoporous lithium titanate lithium ion battery material of a kind of carbon cladding and preparation method thereof.
Carbon provided by the present invention cladding mesoporous lithium titanate lithium ion battery negative material, it is characterised in that this material by
The nanocrystalline particle agglomeration being self-assembly of a diameter of 0.1～10 μm of 5～150nm, has meso-hole structure, and average pore size is
2～6nm, carbon content is 0.5～5%.
This mesoporous lithium titanate anode material can be prepared according to the method comprised the steps:
(1) take the additive of 0.02～2g, be added in organic solution, directly use or take the use of its suspension；
(2) in the solution that step (1) obtains add titanium source so that it is concentration be 0.02～0.5mol/L, after stirring, press
Add lithium-containing compound, stirring at Li: Ti=4: 5；
(3) solution of step (2) gained is loaded in reactor, compactedness 50～80%, carry out heat treatment in an oven,
Heat treatment obtains white depositions after terminating, washing, is dried；
(4) dried sample is placed in protective atmosphere, and calcines certain time at different temperatures, finally obtain
The lithium titanate with meso-hole structure of different-grain diameter, this lithium titanate sample can be as lithium ion battery negative material.
Used in above-mentioned steps (1), additive is the one in glycine, lysine, alanine, glutamic acid, ethanolamine
Or it is several.
Titanium source used in above-mentioned steps (2) is butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride
In one or more；Lithium-containing compound is the one in Lithium hydrate, Quilonorm (SKB), lithium nitrate, lithium chloride, lithium sulfate or several
Kind.
Heat treatment temperature in above-mentioned steps (3) is 150 DEG C～240 DEG C, and the response time is 8～72 hours.
The mixed gas that protective atmosphere is argon, nitrogen, argon or nitrogen and hydrogen in above-mentioned steps (4)；Calcining
Temperature is 300～900 DEG C, and calcination time is 0.5～72 hour.
The present invention utilizes the process characteristic of solvent thermal, by Optimizing Process Parameters, adjusts reactant and solvent species, passes through
Heat treatment, it is thus achieved that the mesoporous lithium titanate of carbon cladding, and this lithium titanate has part titanous.In prepared by the present invention, additive
Play three below effect: (1) additive id reaction or produce water, the beneficially hydrolysis in titanium source with solvent reaction；(2) add
Agent id reaction or with solvent reaction produce Organic substance, absorption on the surface of lithium titanate particle, prevent particle agglomeration；(3) also
In originality atmosphere during heat treatment, adsorb the organic carbon at particle surface, the Ti in lithium titanate simultaneously4+Partial reduction becomes Ti3 +.Present invention preparation has the mesoporous lithium titanate of carbon cladding, and chemical composition is homogeneous, and specific surface area is big, carbon cladding and part titanous
Being conducive to lithium ion and the migration of electronics, its charge/discharge capacity under high magnification is higher, and coulombic efficiency, close to 100%, shows
Excellent chemical property.By controlling the addition of additive, regulation reaction temperature and time, Jie of carbon cladding can be controlled
The particle size range (0.1～10 μm) of hole lithium titanate and the content (0.5～5%) of carbon.Technical process is simple, and preparation parameter is easy
In control, reproducible, can synthesize with scale.
The mesoporous lithium titanate material of the carbon cladding of the present invention can be used as the negative material of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of the mesoporous lithium titanate of carbon cladding in embodiment 1.
Fig. 2 is the stereoscan photograph of the mesoporous lithium titanate entirety pattern of carbon cladding in embodiment 1.
Fig. 3 is the graph of pore diameter distribution of the mesoporous lithium titanate of carbon cladding in embodiment 1.
Fig. 4 is the electron paramagnetic resonance spectrum of the mesoporous lithium titanate of carbon cladding in embodiment 1.
Fig. 5 is the mesoporous lithium titanate of the carbon cladding charging and discharging curve when 2C in embodiment 1.
Fig. 6 is the mesoporous lithium titanate of the carbon cladding charging and discharging curve when 20C in embodiment 1.
Detailed description of the invention
The main implementation process of the present invention is:
(1) taking a certain amount of additive, be dissolved in organic solution, the amount of additive is 0.02～2g, directly uses
Or take the use of its suspension；
(2) in the solution obtained, add a certain amount of titanium source so that it is concentration be 0.02～0.5mol/L, after stirring, press
Add lithium-containing compound at Li: Ti=4: 5, stirs a period of time；
(3) being loaded in reactor by the solution of gained, compactedness is 50～80%, carries out heat treatment in an oven, controls
Temperature is between 150 DEG C～240 DEG C, and successive reaction is 8～72 hours, and heat treatment obtains white color precipitate after terminating, wash,
It is dried；
(4) by dried sample respectively under the mixed atmosphere of argon, nitrogen, argon or nitrogen and hydrogen is protected,
Calcine 0.5～72 hours between 300～900 DEG C, finally obtain the mesoporous lithium titanate of the carbon cladding of different-grain diameter, this lithium titanate
Sample can be as lithium ion battery negative material.
It is further elucidated with the feature of the present invention by the following examples, but is not limited to embodiment.
Experimental technique in following embodiment, if no special instructions, is conventional method.
Embodiment 1:
Under agitation joining in 60mL dehydrated alcohol by 1.2g glycine, stir 1h, stand 20min subsequently, it is heavy to remove
Form sediment, take upper strata suspension standby.Under agitation the butyl titanate of 3ml is added in suspension, stir 1h, add
0.2961g Lithium hydrate, stirs 2h.Being poured into by the solution of acquisition in the reactor that capacity is 100ml, compactedness is 60%,
Baking oven reacts 20h in 200 DEG C.After room temperature is down to by question response still, collects product, and product is used ethanol centrifuge washing, finally
Product after washing is put into baking oven, the most i.e. obtains the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance in a nitrogen atmosphere 500
DEG C calcining 2h, obtain Lycoperdon polymorphum Vitt lithium titanate powder.Its Fig. 1 is the X-ray diffracting spectrum of lithium titanate powdery prepared by this embodiment,
From collection of illustrative plates it can be seen that its thing to be the lithium titanate crystallinity of cubic spinel structure mutually good.By elementary analysis, obtain it and contain
Carbon amounts is 0.78%.Fig. 2 is the photo of this powder body overall pattern under JEOL JSM-6700 type field emission scanning electron microscope, can
To find out that this powder granule varies, little granule is about about 100nm, and bulky grain is about about 1～3 μm, by 20nm
The nanocrystalline composition of left and right.Fig. 3 is the graph of pore diameter distribution of gained sample, and as can be seen from Figure, sample is meso-hole structure, aperture
It is distributed between 3～5nm.Fig. 4 is the electron paramagnetic resonance spectrum of gained sample, as seen from the figure, sample have Lacking oxygen and
Ti3+Signal.By equal to this powder body, conductive carbon black and binding agent PVDF (Kynoar) in mass ratio 7: 1.5: 1.5 mixed grinding
Even, it is subsequently adding appropriate solvent NMP (N-Methyl pyrrolidone), is evenly applied on Copper Foil after mixing well pulping, vacuum at 100 DEG C
Drying obtains pole piece.With metal lithium sheet for pole, 1mol L-1 LiPF6/ EC+DMC+EMC (volume ratio 1: 1: 1) is electrolyte,
Polypropylene material is barrier film, is assembled into 2025 type button cells in the glove box of full argon.Use LAND CT2001A electricity
Pond test system, carries out charge-discharge test with constant electric current density, and charging/discharging voltage scope is between 1～3V, and discharge and recharge is electric
Current density is 335mA g-1(2C).Fig. 5 and Fig. 6 is the charge-discharge test curve obtained, it can be seen that this material is made
Showing the chemical property of excellence during for the negative pole of lithium ion battery, its first discharge specific capacity is 173.3mAh g-1, fill
Electricity specific capacity is 171.0mAh g-1, closely its theoretical capacity 175mAh g-1.After 200 discharge and recharges, it is put
Electricity specific capacity remains 163.3mAh g-1.When charging and discharging currents density is 3350mA g-1(20C) time, its ratio that discharges first
Capacity is 146mAh g-1, charge specific capacity is 138.2mAh g-1, after 200 discharge and recharges, its specific discharge capacity is protected
Hold as 135.2mAh g-1。
Embodiment 2:
Under agitation joining in 60mL dehydrated alcohol by 1.2g glycine, stir 1h, stand 20min subsequently, it is heavy to remove
Form sediment, take upper strata suspension standby.Under agitation the butyl titanate of 3ml is added in suspension, stir 1h, add
0.2961g Lithium hydrate, stirs 2h.Being poured into by the solution of acquisition in the reactor that capacity is 100ml, compactedness is 60%,
Baking oven reacts 20h in 200 DEG C.After room temperature is down to by question response still, collects product, and product is used ethanol centrifuge washing, be dried
Obtain the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance 300 DEG C of calcining 0.5h in a nitrogen atmosphere, obtain Lycoperdon polymorphum Vitt lithium titanate powder
End.X-ray diffracting spectrum result shows, its thing is the lithium titanate of cubic spinel structure mutually.By elementary analysis, obtain it and contain
Carbon amounts is 0.8%.Pass through electron paramagnetic resonance spectrum, it can be seen that sample has Lacking oxygen and Ti3+Signal.Scanning electron microscopic observation is tied
Fruit shows, granule is more uniform, and granule is about about 100nm, by the nanocrystalline composition of about 5nm.The aperture of gained sample
Scattergram shows that sample is meso-hole structure, and pore-size distribution is between 3～6nm.By this powder body, conductive carbon black and binding agent PVDF
(Kynoar) in mass ratio 7: 1.5: 1.5 mixed grinding is uniform, is subsequently adding appropriate solvent NMP (N-crassitude
Ketone), it is evenly applied on Copper Foil after mixing well pulping, at 100 DEG C, vacuum drying obtains pole piece.With metal lithium sheet for pole,
1mol·L-1 LiPF6/ EC+DMC+EMC (volume ratio 1: 1: 1) is electrolyte, and polypropylene material is barrier film, at full argon
2025 type button cells it are assembled in glove box.Use LAND CT2001A battery test system, enter with constant electric current density
Row charge-discharge test, charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mA g-1(2C).Charge and discharge electrical measurement
Test result, shows the chemical property of excellence when this material is as the negative pole of lithium ion battery, its first discharge specific capacity is
174.2mAh·g-1, charge specific capacity is 165.4mAh g-1, after 200 discharge and recharges, its specific discharge capacity keeps
For 151.2mAh g-1.When charging and discharging currents density is 3350mA g-1(20C), time, its first discharge specific capacity is
139.2mAh·g-1, charge specific capacity is 132.4mAh g-1, after 200 discharge and recharges, its specific discharge capacity remains
115.6mAh·g-1。
Embodiment 3:
Under agitation 0.02g lysine is joined in 60mL isopropanol, stir 1h, under agitation by the metatitanic acid of 1.5ml
Four butyl esters are slowly added dropwise in suspension, stir 1h, add 0.2432g lithium nitrate, stir 2h.The solution of acquisition is poured into
Capacity is in the reactor of 100ml, and compactedness is 80%, reacts 72h in 150 DEG C in an oven.After room temperature is down to by question response still,
Collect product, and product is used ethanol centrifuge washing, the most i.e. obtain the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance at nitrogen
The lower 900 DEG C of calcining 72h of atmosphere, obtain Lycoperdon polymorphum Vitt lithium titanate powder.X-ray diffracting spectrum result shows, its thing is that cube point is brilliant mutually
The lithium titanate of stone structure.By elementary analysis, obtaining its phosphorus content is 0.5%.Pass through electron paramagnetic resonance spectrum, it can be seen that sample
There is Lacking oxygen and Ti3+Signal.Scanning electron microscopic observation result shows, this powder granule size is between 7～10 μm, by 150nm
The nanocrystalline composition of left and right.The graph of pore diameter distribution of gained sample shows that sample is meso-hole structure, and pore-size distribution is between 2～3nm.
This powder body, conductive carbon black and binding agent PVDF (Kynoar) in mass ratio 7: 1.5: 1.5 mixed grinding is uniform, then add
Entering appropriate solvent NMP (N-Methyl pyrrolidone), be evenly applied on Copper Foil after mixing well pulping, at 100 DEG C, vacuum drying obtains
Pole piece.With metal lithium sheet for pole, 1mol L-1LiPF6/ EC+DMC+EMC (volume ratio 1: 1: 1) is electrolyte, polypropylene material
Material is barrier film, is assembled into 2025 type button cells in the glove box of full argon.Use LANDCT2001A battery testing system
System, carries out charge-discharge test with constant electric current density, and charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is
335mA·g-1(2C).Charge-discharge test result, shows the electrochemistry of excellence when this material is as the negative pole of lithium ion battery
Can, its first discharge specific capacity is 159.4mAh g-1, charge specific capacity is 158.1mAh g-1, through 200 discharge and recharges
Afterwards, its specific discharge capacity remains 154.6mAh g-1.When charging and discharging currents density is 3350mA g-1(20C), time, it is first
Secondary specific discharge capacity is 129.5mAh g-1, charge specific capacity is 124.3mAh g-1, after 200 discharge and recharges, it is put
Electricity specific capacity remains 120.6mAh g-1。
Embodiment 4:
Under agitation 2g alanine is joined in 60mL ethylene glycol, stir 1h, under agitation by metatitanic acid four isopropyl of 9ml
Ester is slowly added dropwise in suspension, and stirring is lower adds 3.0710g lithium sulfate, stirs 2h.Pouring the solution of acquisition into capacity is
In the reactor of 100ml, compactedness is 70%, reacts 8h in 240 DEG C in an oven.After room temperature is down to by question response still, collects and produce
Thing, and product is used ethanol centrifuge washing, the most i.e. obtain the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance under an argon atmosphere
800 DEG C of calcining 4h, obtain Lycoperdon polymorphum Vitt lithium titanate powder.X-ray diffracting spectrum result shows, its thing is cubic spinel structure mutually
Lithium titanate.By elementary analysis, obtaining its carbon content is 5%.Pass through electron paramagnetic resonance spectrum, it can be seen that it is empty that sample has oxygen
Position and Ti3+Signal.Scanning electron microscopic observation result shows, this powder granule varies, and little granule is about about 300nm, greatly
Granule is about about 4～5 μm, by the nanocrystalline composition of about 35nm.The graph of pore diameter distribution of gained sample shows that sample is Jie
Pore structure, pore-size distribution between 2～4nm by this powder body, conductive carbon black and binding agent PVDF (Kynoar) in mass ratio 7
: 1.5: 1.5 mixed grindings are uniform, are subsequently adding appropriate solvent NMP (N-Methyl pyrrolidone), are evenly applied to after mixing well pulping
On Copper Foil, at 100 DEG C, vacuum drying obtains pole piece.With metal lithium sheet for pole, 1mol L-1LiPF6/ EC+DMC+EMC (volume
Ratio 1: 1: 1) it is electrolyte, polypropylene material is barrier film, is assembled into 2025 type button cells in the glove box of full argon.Adopt
With LAND CT2001A battery test system, carry out charge-discharge test with constant electric current density, charging/discharging voltage scope 1～
Between 3V, charging and discharging currents density is 335mA g-1(2C).Charge-discharge test result, this material bearing as lithium ion battery
Showing the chemical property of excellence during pole, its first discharge specific capacity is 170.1mAh g-1, charge specific capacity is
169.3mAh·g-1, after 200 discharge and recharges, its specific discharge capacity remains 163.6mAh g-1.When discharge and recharge electricity
Current density is 3350mA g-1(20C), time, its first discharge specific capacity is 140.2mAh g-1, charge specific capacity is
135mAh·g-1, after 200 discharge and recharges, its specific discharge capacity remains 130.4mAh g-1。
Embodiment 5:
Under agitation 1.2g glutamic acid is joined in 60mL ethylene glycol, stir 1h, under agitation by the metatitanic acid of 0.27ml
Tetra-ethyl ester is added dropwise in suspension, and stirring is lower adds 0.1228g lithium sulfate, stirs 2h.Pouring the solution of acquisition into capacity is
In the reactor of 100ml, compactedness is 70%, reacts 36h in 200 DEG C in an oven.After room temperature is down to by question response still, collects and produce
Thing, and product is used ethanol centrifuge washing, the most i.e. obtain the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance at argon and hydrogen
Gaseous mixture atmosphere lower 600 DEG C calcining 3h, obtain Lycoperdon polymorphum Vitt lithium titanate powder.X-ray diffracting spectrum result shows, its thing is mutually
The lithium titanate of cubic spinel structure.By elementary analysis, obtaining its phosphorus content is 3.3%.By electron paramagnetic resonance spectrum, permissible
Find out that sample has Lacking oxygen and Ti3+Signal.Scanning electron microscopic observation result shows, this powder granule varies, and little granule is big
Being about about 100nm, bulky grain is about about 2～4 μm, by the nanocrystalline composition of about 25nm.The aperture of gained sample is divided
Butut shows that sample is meso-hole structure, pore-size distribution between 2.5～4.5nm by this powder body, conductive carbon black and binding agent PVDF
(Kynoar) in mass ratio 7: 1.5: 1.5 mixed grinding is uniform, is subsequently adding appropriate solvent NMP (N-crassitude
Ketone), it is evenly applied on Copper Foil after mixing well pulping, at 100 DEG C, vacuum drying obtains pole piece.With metal lithium sheet for pole,
1mol·L-1LiPF6/ EC+DMC+EMC (volume ratio 1: 1: 1) is electrolyte, and polypropylene material is barrier film, at the hands of full argon
2025 type button cells it are assembled in casing.Use LAND CT2001A battery test system, carry out with constant electric current density
Charge-discharge test, charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mA g-1(2C).Charge-discharge test
As a result, showing the chemical property of excellence when this material is as the negative pole of lithium ion battery, its first discharge specific capacity is
170.4mAh·g-1, charge specific capacity is 168.5mAh g-1, after 200 discharge and recharges, its specific discharge capacity keeps
For 161.7mAh g-1.When charging and discharging currents density is 3350mA g-1(20C), time, its first discharge specific capacity is
139mAh·g-1, charge specific capacity is 134.2mAh g-1, after 200 discharge and recharges, its specific discharge capacity remains
128.6mAh·g-1。
Embodiment 6:
Under agitation 0.3g ethanolamine is joined in 60mL isopropanol, stir 1h, under agitation by four chlorinations of 3.3ml
Titanium adds in solution, stirs 1h, adds 1.4498g lithium chloride, stirs 2h.It is 100ml's that the solution of acquisition is poured into capacity
In reactor, compactedness is 50%, reacts 20h in 200 DEG C in an oven.After room temperature is down to by question response still, collect product, and will
Product ethanol centrifuge washing, the most i.e. obtains the former crystalline substance of lithium titanate.By former for the lithium titanate of gained crystalline substance in nitrogen and the mixing of hydrogen
The lower 400 DEG C of calcining 8h of gas atmosphere, obtain Lycoperdon polymorphum Vitt lithium titanate powder.X-ray diffracting spectrum result shows, its thing is a cube point mutually
The lithium titanate of spinel structure.By elementary analysis, obtaining its carbon content is 2.1%.Pass through electron paramagnetic resonance spectrum, it can be seen that sample
Product have Lacking oxygen and Ti3+Signal.Scanning electron microscopic observation result shows, this powder granule varies, and little granule is about
About 100nm, bulky grain is about about 1 μm, by the nanocrystalline composition of about 12nm.The graph of pore diameter distribution of gained sample shows
Sample is meso-hole structure, pore-size distribution between 3～5.5nm by this powder body, conductive carbon black and binding agent PVDF (polyvinylidene fluoride
Alkene) in mass ratio 7: 1.5: 1.5 mixed grindings are uniform, and it is subsequently adding appropriate solvent NMP (N-Methyl pyrrolidone), mixes well pulping
After be evenly applied on Copper Foil, at 100 DEG C, vacuum drying obtains pole piece.With metal lithium sheet for pole, 1mol L-1LiPF6/EC+
DMC+EMC (volume ratio 1: 1: 1) is electrolyte, and polypropylene material is barrier film, is assembled into 2025 in the glove box of full argon
Type button cell.Use LAND CT2001A battery test system, carry out charge-discharge test, discharge and recharge with constant electric current density
Voltage range is between 1～3V, and charging and discharging currents density is 335mA g-1(2C).Charge-discharge test result, this material is as lithium
Showing the chemical property of excellence during the negative pole of ion battery, its first discharge specific capacity is 171.6mAh g-1, charge ratio
Capacity is 167.4mAh g-1, after 200 discharge and recharges, its specific discharge capacity remains 160.2mAh g-1.When filling
Discharge current density is 3350mA g-1(20C), time, its first discharge specific capacity is 143mAh g-1, charge specific capacity is
136.5mAh·g-1, after 200 discharge and recharges, its specific discharge capacity remains 130.4mAh g-1。
Claims (4)
1. carbon cladding a mesoporous lithium titanate lithium ion battery negative material, this material by 5～150nm nanocrystalline self assembly
Forming the particle agglomeration of a diameter of 0.1～10 μm, have meso-hole structure, average pore size is 2～6nm, carbon content be 0.5～
5%, described lithium titanate has Lacking oxygen and titanous, and preparation method comprises the following steps:
(1) take glycine, lysine, alanine, the glutamic acid of 0.02～2g, one or more in ethanolamine are as interpolation
Agent, is dissolved in organic solution, directly uses or takes the use of its suspension；
(2) in the solution that step (1) obtains add titanium source so that it is concentration be 0.02～0.5mol/L, by Li:Ti=4:5
Add lithium-containing compound, stirring；
(3) solution of step (2) gained is loaded in reactor, compactedness 50～80%, carry out heat treatment in an oven, at heat
Reason obtains white depositions after terminating, washing, is dried；
(4) dried sample is placed in the protective atmosphere of mixed gas of argon, nitrogen or nitrogen and argon, and
Calcine certain time under different temperatures, finally obtain the lithium titanate of the carbon cladding with meso-hole structure of different-grain diameter, this metatitanic acid
Lithium sample can be as lithium ion battery negative material.
The mesoporous lithium titanate lithium ion battery negative material of carbon the most according to claim 1 cladding, it is characterised in that: described
Titanium source used in preparation process (1) is the one in butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride
Or it is several；Lithium-containing compound is one or more in Lithium hydrate, Quilonorm (SKB), lithium nitrate, lithium chloride, lithium sulfate.
The mesoporous lithium titanate lithium ion battery negative material of carbon the most according to claim 1 cladding, it is characterised in that: described
Heat treatment temperature in step (3) is 150 DEG C～240 DEG C, and the response time is 8～72 hours.
The mesoporous lithium titanate lithium ion battery negative material of carbon the most according to claim 1 cladding, it is characterised in that: described
Calcining heat in synthesis step (4) is 300～900 DEG C, and calcination time is 0.5～72 hour.
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| CN102544468B true CN102544468B (en) | 2016-12-14 |
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| CN106450255B (en) * | 2016-11-05 | 2019-01-29 | 中南大学 | A kind of NiTiO of sodium-ion battery3/ C negative electrode material, preparation and application |
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| "Novel template-free solvothermal synthesis of mesoporous Li4Ti5O12-C microspheres for high power lithium ion batteries";Laifa Shen et al;《Journal of Materials Chemistry》;20110728;第21卷;第14414-14416页 * |
| "Structure and physical properties of Li4Ti5O12 synthesized at deoxidization atmosphere";Ting-Feng Yi et al.;《Ionics》;20110531;第17卷(第1期);第799-803页 * |
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