CN108615873A - It mixes the preparation method of tantalum lithium titanate anode material and mixes tantalum lithium titanate anode material and lithium ion battery - Google Patents
It mixes the preparation method of tantalum lithium titanate anode material and mixes tantalum lithium titanate anode material and lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention provides a kind of preparation method for mixing tantalum lithium titanate anode material and tantalum lithium titanate anode material and lithium ion battery are mixed, is related to technical field of lithium ion.Tantalum lithium titanate precursor is mixed in titanium source, lithium source and tantalum source by the preparation method by the method formation of mixed grinding first, then will mix tantalum lithium titanate precursor with after carbon source mixing and doping, and re-sinter, obtain mixing tantalum lithium titanate anode material；Tantalum is mixed into lithium titanate, will not change the cyclicity of lithium titanate substantially, while the gram volume of lithium titanate anode material also can be improved, and improves the energy density of lithium titanate；In addition, tantalum lithium titanate precursor will be mixed to mix with carbon source, the characteristic of carbon dioxide volatilization is completely converted into sintering process using carbon source, the particle for mixing tantalum lithium titanate anode material that sintering obtains can be made more uniform, can be obtained that micro/nano level is other to mix tantalum lithium titanate anode material without broken process.The present invention also provides mix tantalum lithium titanate anode material and lithium ion battery.
Description
Technical field
The present invention relates to lithium ion battery material technical fields, in particular to the system for mixing tantalum lithium titanate anode material
Preparation Method and mix tantalum lithium titanate anode material and lithium ion battery.
Background technology
Lithium ion battery is included mainly anode, cathode, can be separated with the electrolyte of conducting lithium ions and by positive and negative anodes
Diaphragm.Wherein, ion cathode material lithium is component part particularly important in lithium ion battery.
Currently, lithium ion battery negative material has very much, such as carbon materials, alloy material, lithium titanate etc..Wherein,
Lithium titanate (Li4Ti5O12) it is a kind of composite oxides by lithium metal and low potential transition metals Ti, maximum feature is exactly it
" zero strain ".So-called " zero strain " refers to its crystal embedded or lattice constant and volume change be all very when deviating from lithium ion
It is small, it is less than 1%.In charge and discharge cycles, this " zero strain " can avoid causing due to stretching back and forth for electrode material
Structural damage reduces the special capacity fade of tape loop to improve the cycle performance and service life of electrode, has very
Overcharging resisting well is crossed and puts feature.
Lithium titanate is by its long-life, high security, quickly-chargeable, the advantages that good cycle, it has also become lithium ion
The hot spot of cell negative electrode material area research.But meanwhile that there are electronic conductivities is relatively low for lithium titanate anode material, aerogenesis leads to electricity
Pond expands, it is of high cost the shortcomings of, and the obtained lithium titanate material of conventional sintering process be easy to reunite it is hardened, need it is follow-up broken etc.
Series of processes.Therefore it must attempt to new preparation method and it be modified low to make up its energy density, conductivity is poor, burns
Lithium titanate material after knot is easy the defects of hardened of reuniting.
In view of this, special propose the present invention to solve the above technical problems.
Invention content
First of the present invention is designed to provide a kind of preparation method for mixing tantalum lithium titanate anode material, by by titanium
The mode in source, lithium source and tantalum source mixed grinding, which is adulterated tantalum source into lithium titanate and prepared, mixes tantalum lithium titanate precursor, and metatitanic acid can be improved
The gram volume of lithium titanate cathode material improves the energy density of lithium titanate, while this process is simple, at low cost；Through oversintering
The obtained particle for mixing tantalum lithium titanate anode material is more uniform, can be obtained that micro/nano level is other to mix tantalum titanium without broken process
Sour lithium titanate cathode material.
Second object of the present invention is that providing one kind mixing tantalum lithium titanate anode material, is born using above-mentioned tantalum lithium titanate of mixing
The preparation method of pole material obtains.
Third object of the present invention is to provide a kind of lithium ion battery, including above-mentioned mixes tantalum lithium titanate anode material.
Fourth object of the present invention be to provide a kind of electronic device comprising above-mentioned lithium ion battery, electric tool,
Electric vehicle or power storage system.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
The present invention provides a kind of preparation methods for mixing tantalum lithium titanate anode material, include the following steps：
(a) titanium source, lithium source and tantalum source are mixed, grinding obtains mixing tantalum lithium titanate precursor；
(b) it will mix after tantalum lithium titanate precursor mixes with carbon source, sintering obtains mixing tantalum lithium titanate anode material；
Wherein, sintering temperature is 800-900 DEG C, sintering time 1-6h；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
Further, described to be ground to wet grinding, preferably wet ball grinding in step (a)；
Preferably, it in step (a), is dried after the wet grinding, obtains mixing tantalum lithium titanate precursor, it is described dry
It is dry to be preferably dried in vacuo.
Further, in step (b), the tantalum lithium titanate precursor and the mass ratio of carbon source mixed is (40-60):1, preferably
For (42-58):1, further preferably (45-55):1.
Further, in step (b), the sintering temperature be 810-880 DEG C, preferably 820-850 DEG C, further preferably
It is 830-840 DEG C；
And/or the sintering time is 1.5-5h, preferably 2-4h, further preferably 2-3h；
And/or the sintering atmosphere is air or oxygen.
Further, the chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, wherein 0.05≤x≤
0.1。
Further, the one kind of the lithium source in lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium nitrate or lithium acetate
Or at least two combination；
Preferably, the titanium source is selected from titanium dioxide and/or metatitanic acid；
Preferably, the one kind or at least two of the tantalum source in tantalum pentoxide, three two tantalums of oxidation or tantalum hydroxide
Combination；
Preferably, the group of the one kind or at least two of the carbon source in glucose, maltose, white granulated sugar or sucrose
It closes.
Further, the preparation method for mixing tantalum lithium titanate anode material, includes the following steps：
(a) titanium dioxide, lithium hydroxide and tantalum pentoxide are mixed, wet grinding, it is dry, it obtains before mixing tantalum lithium titanate
Drive body；
(b) tantalum lithium titanate precursor will be mixed to mix with carbon source and after dry grinding, be sintered 2-3h in 830-840 DEG C, obtain
Mix tantalum lithium titanate anode material；
Wherein, the mass ratio for mixing tantalum lithium titanate precursor and carbon source is (40-60):1；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
The present invention also provides one kind mixing tantalum lithium titanate anode material, using the above-mentioned system for mixing tantalum lithium titanate anode material
Preparation Method is prepared.
The present invention also provides a kind of lithium ion battery, including above-mentioned mix tantalum lithium titanate anode material.
The present invention also provides a kind of electronic device, electric tool, electric vehicle or electricity including above-mentioned lithium ion battery
Power storage system.
Compared with prior art, the preparation method provided by the invention for mixing tantalum lithium titanate anode material, to mix tantalum lithium titanate negative
Pole material, lithium ion battery and electric vehicle have the advantage that：
(1) the present invention provides a kind of preparation methods for mixing tantalum lithium titanate anode material, first by titanium source, lithium source and tantalum source
Tantalum lithium titanate precursor is mixed by the method formation of mixed grinding, then will mix tantalum lithium titanate precursor and carbon source mixing and doping
Afterwards, it then is sintered, obtains mixing tantalum lithium titanate anode material；Tantalum is mixed into lithium titanate, will not change lithium titanate material substantially
Cycle performance, while the gram volume of lithium titanate anode material also can be improved, the energy density of lithium titanate is improved, lithium titanate is improved
The technical issues of material gram volume is relatively low, limitation lithium titanate battery energy density；Meanwhile tantalum titanium is mixed using the preparation of the method for grinding
Sour lithium presoma, simple process and low cost are honest and clean；It mixes with carbon source in addition, tantalum lithium titanate precursor will be mixed, is being sintered using carbon source
Be completely converted into the process carbon dioxide volatilization characteristic, may make the particle for mixing tantalum lithium titanate anode material that sintering obtains compared with
It to be uniform, can be obtained that micro/nano level is other to mix tantalum lithium titanate anode material without broken process, improve using conventional sintering
The lithium titanate material that process obtains is easy technical problem hardened, that needs are broken of reuniting.
(2) the present invention provides a kind of preparation method for mixing tantalum lithium titanate anode material, process is simple, easily operated, raw
It produces at low cost, is suitable for industrialized production.
(3) the present invention provides one kind mixing tantalum lithium titanate anode material, is prepared by above-mentioned preparation method.This mixes tantalum
Lithium titanate anode material conductivity is high, has excellent chemical property；
After testing, which is up to 180mAh/g, and 1000
Capacity retention ratio is 98.0% or so after secondary cycle；2C gram volumes are up to 174mAh/g, and capacity retention ratio is after 1000 cycles
89.0% or so.
(4) the present invention provides a kind of lithium ion battery, including above-mentioned tantalum lithium titanate anode material is mixed.Tantalum is mixed in view of above-mentioned
Advantage possessed by lithium titanate anode material so that there is good electrochemistry using its lithium ion battery as negative material
Performance.
(5) the present invention provides the electronic device comprising above-mentioned lithium ion battery, electric tool, electric vehicle or electric power to deposit
Storage system.In view of advantage possessed by above-mentioned lithium ion battery, in the electronics of the lithium ion battery using embodiment of the present invention
Identical effect can also be obtained in device, electric tool, electric vehicle and electric power storage system.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the X ray diffracting spectrum that the embodiment of the present invention 1 mixes tantalum lithium titanate anode material and lithium titanate anode material
(XRD diagram), wherein prepared by a- embodiments 1 mixes tantalum lithium titanate anode material (LTO/Ta), b- lithium titanate anode materials
(LTO)；
Fig. 2 is scanning electron microscope (SEM) figure for mixing tantalum lithium titanate anode material prepared by the embodiment of the present invention 1；
Fig. 3 is Fig. 2 scanning electron microscope (SEM) part (scribe area) enlarged drawing.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the invention, there is provided mixing the preparation method of tantalum lithium titanate anode material, include the following steps：
(a) titanium source, lithium source and tantalum source are mixed, grinding obtains mixing tantalum lithium titanate precursor；
(b) it will mix after tantalum lithium titanate precursor mixes with carbon source, sintering obtains mixing tantalum lithium titanate anode material；
Wherein, sintering temperature is 800-900 DEG C, sintering time 1-6h；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
In the present invention, tantalum source is adulterated into lithium titanate, will not change cyclicity and the safety of lithium titanate material, simultaneously
The gram volume that lithium titanate anode material also can be improved improves the energy density of lithium titanate, improve lithium titanate material gram volume compared with
It is low, the technical issues of to limit lithium titanate battery energy density.
Meanwhile tantalum lithium titanate precursor, more traditional sol-gel method, technique letter are mixed using the preparation of the method for grinding
It is single, it is of low cost.
It is mixed with carbon source in addition, tantalum lithium titanate precursor will be mixed, dioxy is completely converted into sintering process using carbon source
Change the characteristic of carbon volatilization so that the particle for mixing tantalum lithium titanate anode material being sintered is more uniform, is without broken process
It can be obtained that micro/nano level is other to mix tantalum lithium titanate anode material, improve and held using the lithium titanate material that conventional sintering process obtains
The technical problem that hardened, needs of easily reuniting are crushed.
To make carbon source be completely converted into carbon dioxide volatilization in sintering process, sintering temperature and sintering time are needed
It is defined.Typical but non-limiting sintering temperature be 800 DEG C, 810 DEG C, 820 DEG C, 830 DEG C, 840 DEG C, 850 DEG C, 860
DEG C, 870 DEG C, 880 DEG C, 890 DEG C or 900 DEG C.Typical but non-limiting sintering time be 1.5h, 2.0h, 2.5h, 3.0h,
3.5h, 4.0h, 4.5h or 5h.
Sintering temperature is too low or sintering time is too short, and carbon dioxide volatilization, meeting cannot be fully converted by be easy to causeing carbon source
There is part carbon residue to remain in sintering feed surface, to influence finally to mix the granule-morphology of tantalum lithium titanate.If sintering temperature it is too high or
Person's sintering time is long, and it is relatively low to be easy to cause phase purity.Therefore sintering temperature and sintering time need to control in suitable range
It is interior.
It should be noted that the molar ratio between lithium source, titanium source and tantalum source directly influences and mixes each element in tantalum lithium titanate
Molar ratio.
In the present invention, the chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, wherein 0.01≤x≤
0.1, preferably 0.05≤x≤0.1.
Wherein, the typical but non-limiting numerical value of x be 0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,
0.09 or 0.1, the typical but non-limiting chemical formula for mixing tantalum lithium titanate anode material accordingly is Li4Ti4.99Ta0.01O12、
Li4Ti4.98Ta0.02O12、Li4Ti4.97Ta0.03O12、 Li4Ti4.96Ta0.04O12、Li4Ti4.95Ta0.05O12、
Li4Ti4.94Ta0.06O12、Li4Ti4.93Ta0.07O12、 Li4Ti4.92Ta0.08O12、Li4Ti4.91Ta0.09O12Or Li4Ti4.9Ta0.1O12。
As a kind of preferred embodiment of the present invention, in step (a), it is ground to wet grinding, preferably wet ball grinding；
Tantalum source is subjected to wet method doping in a manner of wet grinding, can avoid the agglomeration occurred in raw material mixing so that tantalum source is filled
Divide and be doped in lithium titanate precursor, the more traditional sol gel process of such doping way is simple, at low cost.
High energy ball mill can be used and carry out wet ball grinding, Ball-milling Time can be set, be may generally be according to actual needs
4-8h.Wherein, the quality that zirconium ball is added in mechanical milling process be tantalum source, 2-5 times of titanium source and lithium source gross mass, the grain size of zirconium ball is
1-3mm。
Preferably, it is also dried after wet grinding in step (a), obtains mixing tantalum lithium titanate precursor, drying is excellent
It is selected as being dried in vacuo.Vacuum drying can carry out in vacuum drying chamber.
As a kind of preferred embodiment of the present invention, in step (b), tantalum lithium titanate precursor and the mass ratio of carbon source are mixed
For (40-60):1, preferably (42-58):1, further preferably (45-55): 1.It is typical with carbon source to mix tantalum lithium titanate precursor
But unrestricted mass ratio is 40:1、42:1、45: 1、48:1、50:1、52:1、54:1、55:1、58:1 or 60:1.
There is certain restriction for the doping of carbon source, the doping of carbon source is excessive, may result in sintering feed and exists
Part carbon residue；The doping of carbon source is very few, and mixing the hardened effect of reuniting of tantalum lithium titanate for improvement is not obvious.
As a kind of preferred embodiment of the present invention, in step (b), sintering temperature is 810-880 DEG C, preferably 820-
850 DEG C, further preferably 830-840 DEG C；
And/or sintering time 1.5-5h, preferably 2-4h, further preferably 2-3h；
And/or sintering atmosphere is air or oxygen.
Pass through the restriction to sintering temperature, sintering time and sintering atmosphere so that obtained after sintering to mix tantalum metatitanic acid
The particle of lithium titanate cathode material is more uniform, and pattern is more regular.
As a kind of preferred embodiment of the present invention, lithium source is selected from lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium nitrate
One kind in lithium acetate or at least two combination；
Preferably, titanium source is selected from titanium dioxide and/or metatitanic acid；
Preferably, the group of the one kind or at least two of tantalum source in tantalum pentoxide, three two tantalums of oxidation or tantalum hydroxide
It closes；
Preferably, the combination of the one kind or at least two of carbon source in glucose, maltose, white granulated sugar or sucrose.
Pass through the restriction to lithium source, titanium source, tantalum source and the specific raw material of carbon source so that more easily generate and mix tantalum lithium titanate anode
Material.
As a kind of preferred embodiment of the present invention, lithium source, titanium source and tantalum source are in micron level or Nano grade.
It is allowed to be in micron or Nano grade by controlling lithium source, titanium source and the particle size in tantalum source, to be easier
Control mixes tantalum lithium titanate precursor and mixes the size and shape of tantalum lithium titanate anode material.
As a kind of preferred embodiment of the present invention, the preparation method of tantalum lithium titanate anode material is mixed, including walk as follows
Suddenly：
(a) titanium dioxide, lithium hydroxide and tantalum pentoxide are mixed, wet grinding, it is dry, it obtains before mixing tantalum lithium titanate
Drive body；
(b) tantalum lithium titanate precursor will be mixed to mix with carbon source and after dry grinding, be sintered 2-3h in 830-840 DEG C, obtain
Mix tantalum lithium titanate anode material；
Wherein, the mass ratio for mixing tantalum lithium titanate precursor and carbon source is (40-60):1；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
Pass through the specific restriction of the preparation method to mixing tantalum lithium titanate anode material so that preparation-obtained to mix tantalum metatitanic acid
Lithium titanate cathode material also has good chemical property while with regular pattern.
According to the second aspect of the invention, it additionally provides one kind and mixing tantalum lithium titanate anode material, tantalum is mixed using above-mentioned
The preparation method of lithium titanate anode material is prepared.The half-cell 1C gram volumes for mixing the preparation of tantalum lithium titanate anode material are up to
180mAh/g, 1000 times cycle after capacity retention ratio be 98.0% or so；2C gram volumes are up to 174mAh/g, after 1000 times recycle
Capacity retention ratio is 89.0% or so.
According to the third aspect of the present invention, a kind of lithium ion battery is additionally provided, including above-mentioned mixes tantalum lithium titanate anode
Material.Advantage possessed by tantalum lithium titanate anode material is mixed in view of above-mentioned so that lithium ion battery has same technique effect.
According to the fourth aspect of the present invention, additionally provide the electronic device comprising above-mentioned lithium ion battery, electric tool,
Electric vehicle or power storage system.In view of advantage possessed by above-mentioned lithium ion battery, embodiment of the present invention is being used
Identical effect can also be obtained in the electronic device of lithium ion battery, electric tool, electric vehicle and electric power storage system.
Electronic device is the electricity that (for example, performing music) is performed various functions using lithium ion battery as the power supply of operation
Sub-device.Electric tool is the electric tool for carrying out moving parts (for example, drill bit) using lithium ion battery as driving power.Electricity
Motor-car is the electric vehicle run as driving power by lithium ion battery, and can be other than lithium ion battery
It is also equipped with the automobile (including hybrid electric vehicle) of other driving sources.Electric power storage system is to use lithium ion battery as electric power
The electric power storage system of storage source.For example, in household power stocking system, electric power is made to be stored in the lithium as electric power storage source
In ion battery, and the electric power that consumption is stored in lithium ion battery as needed is can use such as domestic electronic appliances
Various devices.
With reference to specific embodiment and comparative example, the invention will be further described.
Embodiment 1
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, is included the following steps：
(a) by 2.50kg TiO2, 1.63kg LiOHH2O and 282.25g Ta2O5Mixing, and with 16.5kg deionizations
Water is added together to high energy ball mill and carries out wet ball grinding batch mixing, mixing time 6h, using vacuum drying chamber by above-mentioned slurry
Drying, obtains mixing tantalum lithium titanate precursor；Wherein, the molar ratio of lithium source, titanium source and tantalum source is 4:4.9:0.1, add zirconium ball matter
Amount is 12.02kg, and zirconium spherolite diameter is 1mm or so；
(b) it is 50 in mass ratio that will mix tantalum presoma with sucrose:1 mixing, add it to planetary high-energy ball mill into
After row dry mixed, said mixture is contained in SiC saggars (500g/ saggars), is placed in high temperature box furnace oxygen atmosphere
830 DEG C of sintering 2h, it is Li to obtain chemical formula4Ti4.9Ta0.1O12Mix tantalum lithium titanate anode material；Wherein, oxygen flow amount is
38L/h, heating curve are room temperature to 830 DEG C, and heating rate is 120 DEG C/h, and temperature is down to 100 DEG C or so and is packed into immediately after sintering
Aluminium foil valve bag.
Embodiment 2
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, is included the following steps：
(a) by 3.91kg TiH2O3, 1.19kg Li2CO3With 165.41g Ta2O3Mixing, and with 18.2kg deionized waters
It is added together to high energy ball mill and carries out wet ball grinding batch mixing, mixing time 6h is dried above-mentioned slurry using vacuum drying chamber
It is dry, it obtains mixing tantalum lithium titanate precursor；Wherein, the molar ratio of lithium source, titanium source and tantalum source is 4:4.95:0.05, add zirconium ball matter
Amount is 18.12kg, and zirconium spherolite diameter is 1mm or so；
(b) it is 50 in mass ratio that will mix tantalum presoma with sucrose:1 mixing, add it to planetary high-energy ball mill into
After row dry mixed, said mixture is contained in SiC saggars (500g/ saggars), is placed in high temperature box furnace oxygen atmosphere
830 DEG C of sintering 2h, it is Li to obtain chemical formula4Ti4.95Ta0.05O12Mix tantalum lithium titanate anode material；Wherein, oxygen flow amount is
38L/h, heating curve are room temperature to 830 DEG C, and heating rate is 120 DEG C/h, and temperature is down to 100 DEG C or so and is filled immediately after sintering
Enter aluminium foil valve bag.
Embodiment 3
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, is included the following steps：
(a) by 3.91kg TiH2O3, 1.19kg Li2CO3With 165.41g Ta2O3Mixing, and with 18.2kg deionized waters
It is added together to high energy ball mill and carries out wet ball grinding batch mixing, mixing time 5h is dried above-mentioned slurry using vacuum drying chamber
It is dry, it obtains mixing tantalum lithium titanate precursor；Wherein, the molar ratio of lithium source, titanium source and tantalum source is 4:4.95:0.05, add zirconium ball matter
Amount is 18.12kg, and zirconium spherolite diameter is 1mm or so；
(b) it is 40 in mass ratio that will mix tantalum presoma with glucose:1 mixing, adds it to planetary high-energy ball mill
After carrying out dry mixed, said mixture is contained in SiC saggars (500g/ saggars), is placed in high temperature box furnace oxygen atmosphere
In 800 DEG C sintering 3h, obtain chemical formula be Li4Ti4.95Ta0.05O12Mix tantalum lithium titanate anode material；Wherein, oxygen flow amount
For 36L/h, heating curve is room temperature to 800 DEG C, and heating rate is 100 DEG C/h, and temperature is down to 100 DEG C or so and is filled immediately after sintering
Enter aluminium foil valve bag.
Embodiment 4
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, in addition to sintering temperature in step (b)
It it is 900 DEG C, remaining preparation process and technological parameter are same as Example 3.
Embodiment 5
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, in addition to sintering time in step (b)
For 6h, remaining preparation process and technological parameter are same as Example 3.
Embodiment 6
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, in addition to mixing tantalum forerunner in step (b)
Body is 60 with glucose quality ratio:1, remaining preparation process and technological parameter are same as Example 3.
Embodiment 7
A kind of preparation method for mixing tantalum lithium titanate anode material is present embodiments provided, is included the following steps：
(a) by 2.0kg TiH2O3, 1.07kg LiOHH2O and 10.89g Ta (OH)5Mixing, and with 18.2kg go from
Sub- water is added together to high energy ball mill and carries out wet ball grinding batch mixing, mixing time 5h, using vacuum drying chamber by above-mentioned slurry
Material drying, obtains mixing tantalum lithium titanate precursor；Wherein, the molar ratio of lithium source, titanium source and tantalum source is 4:4.99:0.01, add zirconium
Ball quality is 18.12kg, and zirconium spherolite diameter is 1mm or so；
(b) it is 45 in mass ratio that will mix tantalum presoma with glucose:1 mixing, adds it to planetary high-energy ball mill
After carrying out dry mixed, said mixture is contained in SiC saggars (500g/ saggars), is placed in high temperature box furnace oxygen atmosphere
In 850 DEG C sintering 5h, obtain chemical formula be Li4Ti4.99Ta0.01O12Mix tantalum lithium titanate anode material；Wherein, oxygen flow amount
For 40L/h, heating curve is room temperature to 850 DEG C, and heating rate is 110 DEG C/h, and temperature is down to 100 DEG C or so immediately after sintering
It is packed into aluminium foil valve bag.
Comparative example 1
A kind of preparation method for lithium titanate anode material that this comparative example provides, in addition to being not added with tantalum source in step (a),
Remaining step is same as Example 1.
Comparative example 2
A kind of preparation method for mixing tantalum lithium titanate anode material that this comparative example provides, includes the following steps：
(a) by 2.50kg TiO2With 1.63kg LiOHH2O is added separately in alcohol dispersant, makes it at normal temperatures
Dissolving mixes two kinds of solution and acetic acid is added, 282.25g Ta are then added under stirring conditions2O5；By mixed solution plus
For heat to 65 DEG C, constant temperature 6h obtains gel；It is then dried at 100 DEG C, obtains mixing tantalum lithium titanate precursor；
Step (b) is same as Example 1.
Comparative example 3
A kind of preparation method for mixing tantalum lithium titanate anode material that this comparative example provides, in addition to being not added with sugarcane in step (b)
Sugar is used as carbon source, remaining step and technological parameter are same as Example 1.
Comparative example 4
A kind of preparation method for mixing tantalum lithium titanate anode material that this comparative example provides, in addition to sintering temperature in step (b)
It it is 750 DEG C, remaining step and technological parameter are same as Example 3.
Comparative example 5
A kind of preparation method for mixing tantalum lithium titanate anode material that this comparative example provides, in addition to sintering temperature in step (b)
It it is 920 DEG C, remaining step and technological parameter are same as Example 3.
To verify the effect of embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
XRD and SEM tests are carried out to the tantalum lithium titanate anode material of mixing that each embodiment is prepared.Wherein, only to implement
It is illustrated for example 1.
Fig. 1 is the XRD diagram for mixing tantalum lithium titanate anode material prepared by embodiment 1.From figure 1 it appears that mixing tantalum metatitanic acid
The XRD curves that lithium mixes tantalum lithium titanate (LTO/Ta) coincide substantially with lithium titanate (LTO) standard diagram (PDF NO.49-0207), main
Peak intensity is than more prominent, and substantially without miscellaneous peak, and diffraction maximum is deviated to low angle, this may be the doping due to tantalum element, draw
The variation of lattice is played.It can be seen that regular, the crystallinity of mixing tantalum lithium titanate anode material lattice of preparation by the test result of Fig. 1
Preferably.
Fig. 2 is the SEM figures that tantalum lithium titanate anode material is mixed in embodiment 1, and Fig. 3 is the partial enlarged view of Fig. 2.By Fig. 2 and 3
In as can be seen that it is the neat nearly spherical particle of micro/nano level, rule to mix tantalum lithium titanate material, particle is loosely apparent without occurring
Agglomeration, this explanation can be very good control particle using the preparation method provided by the invention for mixing tantalum lithium titanate anode material
Pattern reduces particle agglomeration.
Meanwhile tantalum lithium titanate anode material or lithium titanate anode material are mixed for what each embodiment and comparative example obtained, it adopts
Its particle D90 is tested with Malvern ParticleSizer, its tap density and specific surface area, concrete outcome are tested using tap density meter
It is shown in Table 1.
1 each embodiment and comparative example particle D90 of table, tap density and specific area measuring result
It can be seen from data in table 1 the obtained grain graininess for mixing tantalum lithium titanate anode material of embodiment 1-7, shake
Real density and specific surface area are integrally better than comparative example 1-5.
Wherein, embodiment 4-6 is the control experiment of embodiment 3, and comparative example 4 and 5 is the contrast experiment of embodiment 3.By table
Data can be seen that in the framework of the present definition in 1, sintering temperature, sintering time and mix tantalum presoma and glucose
Mass ratio influences less for mixing grain size, tap density and the specific surface area of tantalum lithium titanate anode material.
Comparative example 2 is the contrast experiment of embodiment 1.As different from Example 1, comparative example 2 uses conventional sol gel
Tantalum lithium titanate precursor is mixed in method preparation.It can be seen from data in table 1 tantalum lithium titanate is mixed using what sol-gal process was prepared
Negative material grain diameter is larger, and specific surface area is less than normal.
Comparative example 3 is that the contrast experiment of embodiment 1 is not added with carbon source in comparative example 3 as different from Example 1.From table
1 as can be seen that the grain size for mixing tantalum lithium titanate anode material that is prepared of comparative example 3 is obviously bigger than normal, tap density and specific surface
Product is less than normal.As it can be seen that addition carbon source and mix tantalum presoma in step (b) and mix, be sintered, mixing of being obtained after being sintered can be effectively reduced
The grain diameter of tantalum lithium titanate anode material, and then improve tap density and specific surface area.
Experimental example 2
Embodiment 1-7 and comparative example 1-5 negative materials are prepared into button cell respectively, and using blue electric tester to it
Chemical property is tested, and specific preparation method is as follows：
Tantalum lithium titanate anode material or lithium titanate anode material and superconduction carbon black are mixed by prepared by each embodiment and comparative example
Mixing prepares negative electrode diaphragm to binder by a certain percentage, and then dry, slice is prepared into negative plate；Using metal lithium sheet as
Positive plate, C1garde is as diaphragm, using 1M LiPF6- EC/DMC (volume ratios 1:1) it is used as electrolyte, full of argon gas
Glove box in assemble button cell.
The specific test result of embodiment 1-7 and comparative example 1-5 is shown in Table 2 and 3.
Discharge performance and cycle performance under 2 each embodiment and comparative example difference charge-discharge magnification of table
Discharge performance and cycle performance under 3 each embodiment and comparative example difference charge-discharge magnification of table
As can be seen that the charge-discharge parameter for mixing tantalum lithium titanate anode material of embodiment 1-7 offers is apparent from table 2 and 3
Tantalum lithium titanate anode material or lithium titanate anode material are mixed better than what comparative example 1-5 was provided.
Wherein, comparative example 1 is the contrast experiment of embodiment 1, the two the difference is that be not added with tantalum source in comparative example 1,
It is lithium titanate anode material that i.e. comparative example 1, which is prepared, and it is to mix tantalum lithium titanate anode material that embodiment 1, which is prepared,.
Electric discharge gram volume can effectively be promoted by mixing tantalum into lithium titanate it can be seen from table 2 and 3, while have substantially no effect on material
Cycle performance.
Comparative example 2 is the contrast experiment of embodiment 1.Difference from Example 1 is that comparative example 2 uses conventional sol
Tantalum lithium titanate precursor is mixed in gel method preparation.Data can be seen that using preparation method system provided by the invention from table 2 and 3
The standby obtained charge and discharge gram volume mixed under tantalum lithium titanate anode material different multiplying and cycle efficieny are obviously improved.
Comparative example 3 is that the contrast experiment of embodiment 1 is not added with carbon source in comparative example 3 as different from Example 1.From table
In 2 and 3 as can be seen that comparative example 3 be prepared mix the discharge performance under tantalum lithium titanate anode material different multiplying and follow
Ring performance is inferior to the embodiment of the present invention 1.It can be seen that the addition of carbon source is conducive to optimization to mix tantalum lithium titanate negative in sintering process
The physical property of pole material also improves its chemical property.
Comparative example 4 and 5 is the contrast experiment of embodiment 3, and the sintering temperature or sintering time of the two are limited beyond the present invention
Numberical range.Only sintering temperature or sintering time is obtained in the framework of the present definition it can be seen from table 2 and 3
The chemical property for mixing tantalum lithium titanate anode material can be only achieved higher level.
In conclusion it is simple using the preparation method process provided by the invention for mixing tantalum lithium titanate anode material, it is easy to grasp
Make, production cost is low, is suitable for industrialized production, and obtained tantalum lithium titanate anode material pattern of mixing is uniform, while have compared with
High gram volume and good cycle performance.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method for mixing tantalum lithium titanate anode material, which is characterized in that include the following steps：
(a) titanium source, lithium source and tantalum source are mixed, grinding obtains mixing tantalum lithium titanate precursor；
(b) it will mix after tantalum lithium titanate precursor mixes with carbon source, sintering obtains mixing tantalum lithium titanate anode material；
Wherein, sintering temperature is 800-900 DEG C, sintering time 1-6h；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
2. preparation method according to claim 1, which is characterized in that it is described to be ground to wet grinding in step (a), it is excellent
It is selected as wet ball grinding；
Preferably, it is also dried after wet grinding described in step (a), obtains mixing tantalum lithium titanate precursor, the drying
Preferably it is dried in vacuo.
3. preparation method according to claim 1, which is characterized in that in step (b), it is described mix tantalum lithium titanate precursor with
The mass ratio of carbon source is (40-60):1, preferably (42-58):1, further preferably (45-55):1.
4. preparation method according to claim 1, which is characterized in that in step (b), the sintering temperature is 810-880
DEG C, preferably 820-850 DEG C, further preferably 830-840 DEG C；
And/or the sintering time is 1.5-5h, preferably 2-4h, further preferably 2-3h；
And/or the sintering atmosphere is air or oxygen.
5. preparation method according to claim 1, which is characterized in that the chemical formula for mixing tantalum lithium titanate anode material is
Li4Ti5-xTaxO12, wherein 0.05≤x≤0.1.
6. according to the preparation method described in claim 1-5 any one, which is characterized in that the lithium source is selected from lithium carbonate, carbon
Sour hydrogen lithium, lithium hydroxide, lithium nitrate or one kind in lithium acetate or at least two combination；
Preferably, the titanium source is selected from titanium dioxide and/or metatitanic acid；
Preferably, the group of the one kind or at least two of the tantalum source in tantalum pentoxide, three two tantalums of oxidation or tantalum hydroxide
It closes；
Preferably, the combination of the one kind or at least two of the carbon source in glucose, maltose, white granulated sugar or sucrose.
7. according to the preparation method described in claim 1-5 any one, which is characterized in that include the following steps：
(a) titanium dioxide, lithium hydroxide and tantalum pentoxide are mixed, wet grinding, it is dry, it obtains mixing tantalum lithium titanate forerunner
Body；
(b) tantalum lithium titanate precursor will be mixed to mix with carbon source and after dry grinding, be sintered 2-3h in 830-840 DEG C, obtain mixing tantalum
Lithium titanate anode material；
Wherein, the mass ratio for mixing tantalum lithium titanate precursor and carbon source is (40-60):1；
The chemical formula for mixing tantalum lithium titanate anode material is Li4Ti5-xTaxO12, 0.01≤x≤0.1.
8. one kind mixing tantalum lithium titanate anode material, which is characterized in that mix tantalum metatitanic acid using described in claim 1-7 any one
The preparation method of lithium titanate cathode material is prepared.
9. a kind of lithium ion battery, which is characterized in that mix tantalum lithium titanate anode material including according to any one of claims 8.
10. electronic device, electric tool, electric vehicle comprising the lithium ion battery described in claim 9 or electric power storage system
System.
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| CN111082022A (en) * | 2019-12-28 | 2020-04-28 | 石家庄昭文新能源科技有限公司 | High-rate spherical oxide alloy composite electrode material and preparation method thereof |
| CN111129472A (en) * | 2019-12-31 | 2020-05-08 | 湘潭大学 | Ti0.51Ta0.49O2Preparation method of-C nanofiber negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111082022A (en) * | 2019-12-28 | 2020-04-28 | 石家庄昭文新能源科技有限公司 | High-rate spherical oxide alloy composite electrode material and preparation method thereof |
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