CN102339999A - Polyanion composite material, its preparation method and application - Google Patents

Polyanion composite material, its preparation method and application Download PDF

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Publication number
CN102339999A
CN102339999A CN2010102307834A CN201010230783A CN102339999A CN 102339999 A CN102339999 A CN 102339999A CN 2010102307834 A CN2010102307834 A CN 2010102307834A CN 201010230783 A CN201010230783 A CN 201010230783A CN 102339999 A CN102339999 A CN 102339999A
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composite material
boron
nitrogen
carbon
weight percentage
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CN102339999B (en
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胡勇胜
李泓
王兆翔
黄学杰
陈立泉
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Institute of Physics of CAS
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Institute of Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a polyanion composite material, which has a general formula of BxCyNz-LiaD' bMcD'' dXOeAf, with BxCyNz as a compound of boron and carbon, or carbon and nitrogen, or boron, carbon and nitrogen. The invention provides a preparation method of the composite material and its application. The invention also provides a positive electrode with the composite material of the invention and a lithium battery containing the positive electrode. The composite material provided in the invention has high electronic conductivity and ionic conductivity, especially has an excellent rate performance and good cycle stability.

Description

A kind of polyanion composite material
Technical field
The present invention relates to a kind of polyanion composite material, particularly, the present invention relates to a kind of polyanion composite material that contains boron carbon or carbon nitrogen or boron carboritride.
Background technology
Lithium ion battery has been widely used in various portable sets at present; And small lot has been used for electric motor car and energy-storage battery group etc.; These application are also increasingly high to each item performance demands of lithium ion battery simultaneously, such as high-energy-density, high power density, high rate performance, cyclical stability, fail safe etc.The positive electrode of using in the commodity battery at present is mainly LiCoO 2, LiMn 2O 4Deng, negative pole is mainly the graphite-like material with carbon element.The LiFePO with olivine-type (Olivine) of people such as Goodenough discovery in 1997 4As the representative of phosphate cathode material, this material has plurality of advantages such as low price, specific capacity height, long service life, environmental friendliness and thermal stability height.For example, LiFePO 4One of component Fe environment is caused any harm hardly, caused people's interest with its safe voltage range, excellent cycle performance.LiMPO 4Belong to rhombic system, lithium ion is from LiFePO 4In when deviating from fully, volume-diminished 6.81%.Compare LiFePO with other anode material for lithium-ion batteries 4Itself be insulator, its intrinsic conductivity is low by (10 -12-10 -9S cm -1), Li +At LiFePO 4In the chemical diffusion coefficient also lower, constant current intermittently the value of titration technique (GITT) and ac impedance technology (AC) mensuration 1.8 * 10 -16-2.2 * 10 -14Cm 2s -1, the capacity of battery will be far below its theoretical capacity when high current charge-discharge.
In order to solve lower electronic conductivity and ionic diffusion coefficient problem, mainly contain three kinds of methods at present: first method is to reduce the particle scale of material or form a kind of porous material; Second method is that heteroatom mixes, like Na +, Mg 2+The doping of ion etc.; Or formation oxygen room (seeing also Chinese patent ZL 200410037502.8 and ZL 200410101618.3); The third method is carbon to be carried out on the material granule surface coat.At present, the carbon coating technology is widely used in the modification of lithium ion battery positive and negative electrode material, only contains carbon in the coating layer.Be typically LiFePO the most 4, people such as Armand M. disclose LiFePO 4The method of coated with carbon (with reference to Ravet N, Chouinard Y, Magnan JF, Besner S; Gauthier M, Armand M, JOURNAL OF POWER SOURCES; 97-8:503-507,2001, and one Chinese patent application 200810149531.1); Improve the electronics contact between the particle, improved the electronic conductivity of material, greatly improved LiFePO 4Chemical property, become the necessary condition of its commercial applications.
Though these improve the multiplying power property of having improved material really, in the practical application of battery, particularly in the application of high-power and long-life batteries; When for example surpassing the discharging and recharging of 10C (be equivalent to 6 minutes batteries fill entirely entirely put); Require the high rate performance of material very high, capability retention must require to circulate in more than several thousand times more than 80% simultaneously; This just requires electrode material to have higher electronic conductance and ionic conductance simultaneously; And good electrical contact between the maintenance particle, also high interface stability to be arranged, and adopt the above-mentioned material that obtains of improving one's methods can not satisfy above requirement.
Summary of the invention
The objective of the invention is in order to overcome existing LiFePO 4Electronics and ionic conductivity Deng polyanion class material during as positive pole material of secondary lithium battery are low; Adopt present existing technical method can not improve the shortcoming of the high rate performance and the cycle performance of material simultaneously; Thereby a kind of polyanion composite material is provided, and this composite material forms B through the high conductive compound that introducing contains boron carbon or carbon nitrogen or boron carbon nitrogen xC yN z-Li aD ' bM cD " dXO eA fComposite material significantly improves the high rate performance and the cycle performance of material.Positive pole and lithium battery that the present invention also provides the preparation method and the purposes of above-mentioned composite material and adopts above-mentioned Composite Preparation.
Technical scheme of the present invention is following:
A kind of polyanion composite material, this composite material has following general formula: B xC yN z-L aD ' bM cD " dXO eA f,
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is selected from a kind of among Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta and the W;
M is selected from a kind of among Fe, Mn, Co, Ni, Ti and the V;
D " is selected from a kind of among Li, Na, M g, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La and the Ce;
X is selected from a kind of among P, Si, S, B and the C;
A is selected from a kind of among N and the F;
And D ', M and D " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously.
In the above-mentioned composite material, said B xC yN zBe coated on Li aD ' bM cD " dXO eA fThe surface of material granule.
In the above-mentioned composite material, said B xC yN zWeight percentage in said composite material is 0.1%-20%, is preferably 1%-10%.
In the above-mentioned composite material, when x=0, said B xC yN zThe weight percentage of middle nitrogen is 0.001%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0.0001%-10%, is preferably 0.01%-3%; When x ≠ 0, said B xC yN zThe weight percentage of middle nitrogen is 0%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0%-10%, is preferably 0.01%-3%.
In the above-mentioned composite material, when z=0, said B xC yN zThe weight percentage of middle boron is 0.001%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0.0001%-6%, is preferably 0.01%-1%; When z ≠ 0, said B xC yN zThe weight percentage of middle boron is 0%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0%-10%, is preferably 0.01%-1%.
The present invention also provides the preparation method of above-mentioned composite material, and this preparation method is selected from coating method or mechanical ball milling method.
Wherein, said coating method comprises the steps:
(1) with L aD ' bM cD " dXO eA fWith the ionic liquid that contains boron carbon or carbon nitrogen or boron carbon nitrogen, for example [EMIm] [N (CN) 2] (1-ethyl-3-methylimidazolium dicyanamide) or other organic compound mixed in blender 5-30 minute, obtains the mixture of the two
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is selected from a kind of among Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta and the W;
M is selected from a kind of among Fe, Mn, Co, Ni, Ti and the V;
D " is selected from a kind of among Li, Na, M g, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La and the Ce;
X is selected from a kind of among P, Si, S, B and the C;
A is selected from a kind of among N and the F;
And D ', M and D " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) obtains is warming up to 600 ℃ from room temperature, and under this temperature, kept 2 hours with 2 ℃/minute speed, make the abundant cracking of ionic liquid, obtain said composite material after the cooling.
The present invention also provides above-mentioned composite material in preparation electrode material of lithium battery, the for example purposes in the positive electrode.
The present invention also provides a kind of positive pole, and this positive pole comprises collector and load on the positive electrode on this collector that said positive electrode contains above-mentioned composite material.
The present invention also provides a kind of lithium battery, and this battery comprises positive pole, negative pole and electrolyte, the said just very above-mentioned positive pole that contains composite material of the present invention.
It below is detailed description of the present invention.
The present invention provides a kind of polyanion composite material, and its general formula is: B xC yN z-Li aD ' bM cD " dXO eA f,
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta, W;
M is Fe, Mn, Co, Ni, Ti, V;
D " be Li, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La, Ce;
X is P, Si, S, B, C;
A is N, F;
And M and M " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously.
According to the present invention, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound, Li aD ' bM cD " dXO eA fBe active electrode material, be preferably LiFePO 4The present invention contains the high conductive compound of boron carbon or carbon nitrogen or boron carbon nitrogen through interpolation; Can improve the electronic conductivity of composite material on the one hand; Can reduce on the other hand lithium ion its active material with contain boron carbon or carbon nitrogen or boron carboritride migration activation energy at the interface; Thereby improve lithium ion at the interface ionic conductivity, improved the high rate performance of composite material.The best effect of composite material of the present invention is with containing boron carbon or carbon nitrogen or boron carbon nitrogen compound is coated on LiFePO 4On the surface of polyanion class material granule, improved interface stability like this, and then improved the cycle life of composite material.
In the present invention, said boron carbon or carbon nitrogen or the boron carbon nitrogen compound B of containing xC yN zCan be coated on active electrode material Li aD ' bM cD " dXO eA fThe surface, this can improve interface stability, and then improves the cycle life of composite material.
In the present invention, said B xC yN zWeight percentage in said composite material is 0.1%-20%, is preferably 1%-10%.
In the present invention, when x=0, said B xC yN zThe weight percentage of middle nitrogen is 0.001%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0.0001%-10%, is preferably 0.01%-3%; When x ≠ 0, said B xC yN zThe weight percentage of middle nitrogen is 0%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0%-10%, is preferably 0.01%-3%.
In the present invention, when z=0, said B xC yN zThe weight percentage of middle boron is 0.001%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0.0001%-6%, is preferably 0.01%-1%; When z ≠ 0, said B xC yN zThe weight percentage of middle boron is 0%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0%-10%, is preferably 0.01%-1%.
It is conductivity, high rate performance and cycle life in order to improve composite material that the present invention selects specific proportioning and composition.
The present invention also provides the preparation method of above-mentioned composite material, and this preparation method can comprise the steps:
(1) with L aD ' bM cD " dXO eA fWith the ionic liquid that contains boron carbon or carbon nitrogen or boron carbon nitrogen, for example [EMIm] [N (CN) 2] or other organic compound in blender, mixed 5-30 minute, obtain the mixture of the two
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is selected from a kind of among Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta and the W;
M is selected from a kind of among Fe, Mn, Co, Ni, Ti and the V;
D " is selected from a kind of among Li, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La and the Ce;
X is selected from a kind of among P, Si, S, B and the C;
A is selected from a kind of among N and the F;
And D ', M and D " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) obtains is warming up to 600 ℃ from room temperature, and under this temperature, kept 2 hours with 2 ℃/minute speed, make the abundant cracking of ionic liquid, obtain said composite material after the cooling.
In one embodiment of the invention, it is specific as follows that the present invention prepares the method for composite material:
(1) takes by weighing an amount of active electrode material powder; For example be put in the centrifuge tube,, get the ionic liquid or other organic compound that contain boron carbon or carbon nitrogen or boron carbon nitrogen in required ratio; The adding powder is placed in the shaker mixer and vibrated 5 to 30 minutes; Ionic liquid and active electrode material are fully mixed, look the difference of ionic liquid additional proportion, obtain mixture for doing wet degree different powder/grains of sand shape/gunk; And
(2) at tube furnace, in argon gas or the nitrogen atmosphere, be warming up to 600 ℃/min with the speed of 2 ℃/min from room temperature, kept 2 hours at 600 ℃/min, make the abundant cracking of ionic liquid, treat that tube furnace cooling back takes out sample, it is subsequent use to put into drier after the grinding.Sample behind the sintering is looked the difference that adds the ionic liquid ratio, and color is grey black to black.
The preparation method who more than describes is the coating method, is total to knowledge like this area, and those of ordinary skills also can adopt other preparation method, and for example the mechanical ball milling method waits and prepares above-mentioned composite material of the present invention.
The present invention also provides above-mentioned composite material in preparation electrode material of lithium battery, the for example purposes in the positive electrode.
The present invention also provides a kind of positive pole, and this positive pole comprises collector and load on the positive electrode on this collector that said positive electrode contains above-mentioned composite material.Because the present invention only relates to the improvement to composite, the preparation method of positive pole and the composition of positive pole are not particularly limited, adopt the conventional preparation method in this area to get final product with forming.Described collector can adopt all available plus plate current-collecting bodies known in the art, and there is no particular limitation to it in the present invention.
The present invention also provides a kind of lithium battery, and this battery comprises positive pole, negative pole and electrolyte, the said just very above-mentioned positive pole that contains composite material of the present invention.
Particularly, the present invention can be used for above-mentioned composite material the positive electrode of serondary lithium battery, processes the positive pole of serondary lithium battery, forms serondary lithium battery with negative pole, the electrolyte of routine.Carbon, conducting metal oxide or metal that the conductive additive that uses in the positive pole uses as routine; But the active material that negative pole uses comprises embedding lithium material with carbon element, lithium metal, lithium alloy, spinel lithium titanate or sulfide; Be full of electrolyte between positive pole and the negative pole, positive pole is burn-on respectively to go between with an end of negative pole and is linked to each other with the battery case two ends of mutually insulated.
Adopt polyanion composite material of the present invention to be applicable to that as the above-mentioned serondary lithium battery of positive pole various mobile electronic devices maybe need move the equipment of driven by energy and the deposit or the back-up source of non-moving type, and be not limited to this.
Compared with prior art, the present invention has following beneficial effect at least:
1, the present invention is at LiFePO 4The high conductive compound that contains boron carbon or carbon nitrogen or boron carbon nitrogen Deng introducing in the polyanion class material; Can improve the electronic conductivity of composite material on the one hand; Can reduce on the other hand lithium ion its active material with contain boron carbon or carbon nitrogen or boron carboritride migration activation energy at the interface; Thereby improve lithium ion at the interface ionic conductivity, improved the high rate performance of composite material.
2, the present invention's high conductive compound that will contain boron carbon or carbon nitrogen or boron carbon nitrogen is coated on for example LiFePO 4On the surface of polyanion class material material particle, improved interface stability, and then improved the cycle life of positive electrode.
3, method for coating step of the present invention is simple, has overcome tradition with sucrose solution or polymer solution during as the presoma of carbon, and the problem of the phase-splitting that solvent evaporation brings in heat treatment process/gather causes the inhomogeneous of carbon coating layer.Especially to porous material, covered effect is better.Implementation method of the present invention is simple, and the content of boron carbon nitrogen is controlled easily, is with a wide range of applications.
4. compare with the composite material that only uses carbon containing, use the conductivity of composite material of the high conductive compound that contains boron carbon or carbon nitrogen or boron carbon nitrogen of the present invention good, the lithium battery high rate performance of preparation all is greatly improved with long cyclical stability.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.But these embodiment only limit to explanation
The present invention and be not used in the restriction scope of the present invention.The experimental technique of unreceipted concrete experiment condition in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Under dry atmosphere, will contain ionic liquid [the EMIm] [N (CN) of carbon nitrogen 2] 0.3g adds 1gLiFePO 4Powder, vibration is 30 minutes in shaker mixer, obtains grains of sand shape mixture.This mixture is transferred to alumina crucible, put into tube furnace, logical argon gas or nitrogen.Be warming up to 600 ℃ from room temperature with the speed of 2 ℃/min, kept 2 hours at 600 ℃, make the abundant cracking of ionic liquid, treat that tube furnace cooling back takes out sample, grinding the back is black powder, is composite material of the present invention.Wherein, the weight percentage of nitrogen in carboritride is about 28%, and the weight percentage of carboritride in composite material is about 5%.
With the sample making simulated battery.By the LiFePO before and after coating 4: acetylene black: the ratio of PVdF binding agent=85%: 10%: 5% is mixed the formation slurry at normal temperatures and pressures, evenly is coated on the substrate that aluminium foil is a collector and makes electrode slice, and the film thickness of gained is the 5-30 micron, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, and electrolyte is the LiPF of 1M 6Be dissolved in the mixed solvent of EC and DEC of 1L (volume ratio 1: 1).Positive pole, negative pole, electrolyte are assembled into simulated battery in the glove box of argon shield.The testing procedure of simulated battery: at first the electric current with C/2 discharges and recharges between 2-4.2V, and the capacity of being emitted is the discharge capacity under this multiplying power; Circulate after several weeks, progressively improve the current density that discharges and recharges, up to 10C.The test result of simulated battery is listed in table 1.
Embodiment 2-3
Method by embodiment 1 prepares the polyanion composite material of forming by table 1 that is used for serondary lithium battery of the present invention; Different is; Ionic liquid and content of active substance are different, obtain the composite material of different carboritride weight percentages, are respectively about 2% and 12%.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 4-5
Method by embodiment 1 prepares the polyanion composite material of forming by table 1 that is used for serondary lithium battery of the present invention; Different is; Heat treatment temperature is different, obtains the composite material of the weight percentage of different nitrogen in carboritride, is respectively about 38% and 7%.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 6
The LiFePO that contains carboritride 4Composite material can also be synthetic through following steps.At first, take by weighing Li at 0.5: 1: 1 according to mol ratio 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4, behind the mechanical ball milling, with this mixture again with a certain amount of ionic liquid [EMIm] [N (CN) 2] mix (and mixed proportion be 1 the gram LiFePO 4: 0.3 gram-ion liquid), at high-purity Ar gas or N 2Heat-treat under the protective atmosphere of gas, heat treatment temperature is 650 ℃, this temperature constant temperature 4 hours, naturally cools to room temperature then, obtains containing the LiFePO of carboritride 4Composite material, grinding the back is black powder.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 7-21
By the polyanion composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 1, different is that the polyanion positive electrode of being selected for use is different, has obtained containing the different polyanion composite materials of carboritride.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test voltage scope is adjusted according to different positive electrodes to some extent, and its test result is listed in table 1.
Embodiment 22
Method by embodiment 1 prepares the polyanion composite material of forming by table 1 that is used for serondary lithium battery of the present invention; Different is; The boron carbon source of being selected for use is that the perfluor that is dissolved in propylene carbonate replaces triphenyl borine, has obtained containing the LiFePO of boron carbon compound 4Anode composite material.
Through SEM, the pattern before and after relatively coating is found to coat the back pattern and is not changed; The result of XRD and TEM can know that the crystal structure of sample does not change, and is olivine structural; Can find out that from the result of Raman and XPS the surface has the existence of boron, carbon really, the weight percentage of boron in the boron carbon compound is about 4%.TG result shows that the weight percentage of boron carbon compound in composite material is about 7%.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 23
The LiFePO that contains the boron carbon compound 4Composite material can also be synthetic through following steps.At first, take by weighing Li at 0.5: 1: 1 according to mol ratio 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4, behind the mechanical ball milling, this mixture is replaced triphenyl borine with a certain amount of perfluor that is dissolved in propylene carbonate again mixes that (mixed proportion is 1 gram LiFePO 4: 0.35 gram contains the presoma of boron carbon), at high-purity Ar gas or N 2Heat-treat under the protective atmosphere of gas, heat treatment temperature is 650 ℃, this temperature constant temperature 4 hours, naturally cools to room temperature then, obtains containing the LiFePO of carboritride 4Composite material, grinding the back is black powder.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 24-34
By the polyanion composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 and 22 is formed by table 1, different is that the polyanion positive electrode of being selected for use is different, has obtained containing the different polyanion composite materials of carboritride.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test voltage scope is adjusted according to different positive electrodes to some extent, and its test result is listed in table 1.
Embodiment 35
By the polyanion composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 1, different is that the boron carbon nitrogen source of being selected for use is ionic liquid [BCNIm] [BF 4] (1,3-bis (cyanomethyl) imidazolium fluoroborate), obtained containing the LiFePO of boron carboritride 4Anode composite material.
Through SEM, the pattern before and after relatively coating is found to coat the back pattern and is not changed; The result of XRD and TEM can know that the crystal structure of sample does not change, and is olivine structural; Can find out that from the result of Raman and XPS the surface has the existence of boron, carbon, nitrogen really, the weight percentage of boron in the boron carboritride is about 2%, and the weight percentage of nitrogen in the boron carboritride is about 25%.TG result shows that the weight percentage of boron carboritride in composite material is about 5%.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 36
The LiFePO that contains the boron carboritride 4Composite material can also be synthetic through following steps.At first, take by weighing Li at 0.5: 1: 1 according to mol ratio 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4, behind the mechanical ball milling, with this mixture again with a certain amount of ionic liquid [BCNIm] [BF 4] mix (and mixed proportion be 1 the gram LiFePO 4: 0.26 gram-ion liquid [BCNIm] [BF 4]), at high-purity Ar gas or N 2Heat-treat under the protective atmosphere of gas, heat treatment temperature is 650 ℃, this temperature constant temperature 4 hours, naturally cools to room temperature then, obtains containing the LiFePO of boron carboritride 4Composite material, grinding the back is black powder.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test result is listed in table 1.
Embodiment 37-55
Method by embodiment 1 and 35 prepares the polyanion composite material of forming by table 1 that is used for serondary lithium battery of the present invention; Different is; The polyanion positive electrode of being selected for use is different, has obtained containing the different polyanion composite materials of boron carboritride.
The assembling of the positive pole of simulated battery, negative pole, electrolyte and battery is same as embodiment 1, and its test voltage scope is adjusted according to different positive electrodes to some extent, and its test result is listed in table 1.
The comparative example 1LiFePO before and after embodiment 1 coats 4Performance comparison research
Through SEM, LiFePO before and after comparing embodiment 1 coats 4Pattern, find to coat the back pattern and do not change; The result of XRD and TEM can know that the crystal structure of sample does not change, and is olivine structural; Can find out that from the result of Raman and XPS the surface has the existence of nitrogen, carbon really, the weight percentage of nitrogen in carboritride is about 28%.TG result shows that the weight percentage of carboritride in composite material is about 5%.
For the chemical property of sample before and after the comparative study coating, with the sample making simulated battery.By the LiFePO before and after coating 4: acetylene black: the ratio of PVdF binding agent=85%: 10%: 5% is mixed the formation slurry at normal temperatures and pressures, evenly is coated on the substrate that aluminium foil is a collector and makes electrode slice, and the film thickness of gained is the 5-30 micron, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, and electrolyte is the LiPF of 1M 6Be dissolved in the mixed solvent of EC and DEC of 1L (volume ratio 1: 1).Positive pole, negative pole, electrolyte are assembled into simulated battery in the glove box of argon shield.The testing procedure of simulated battery: at first the electric current with C/2 discharges and recharges between 2-4.2V, and the capacity of being emitted is the discharge capacity under this multiplying power; Circulate after several weeks, progressively improve the current density that discharges and recharges, up to 10C.The test result of simulated battery is listed in table 1.
Result according to table 1 can find out; Sample after carboritride coats has shown higher lithium storage content, high rate performance and cycle performance; Under the high magnification of 5C and 10C; Specific capacity is respectively 147mAh/g and 132mAh/g (capability retention is respectively 92% and 83%), and is merely 81mAh/g and 63mAh/g before coating.The battery of the sample assembling after carboritride coats is grown circulation under the 1C multiplying power, after 800 weeks of circulation, the conservation rate of specific capacity is 91%.This shows that carboritride coats and greatly improved LiFePO 4Conductivity, its high rate performance and long cyclical stability all are greatly improved.
The comparative example 2The only contrast of the chemical property of the sample of carbon containing and composite material of the present invention
For comparative study, we have selected sucrose simultaneously for use is carbon source, and under the cracking condition identical with embodiment 1, the content of control sucrose makes and only contains carbon in the pyrolysis product, and the percentage by weight of carbon in composite material is about 5%.
With the sample making simulated battery.By the LiFePO before and after coating 4: acetylene black: the ratio of PVdF binding agent=85%: 10%: 5% is mixed the formation slurry at normal temperatures and pressures, evenly is coated on the substrate that aluminium foil is a collector and makes electrode slice, and the film thickness of gained is the 5-30 micron, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, and electrolyte is the LiPF of 1M 6Be dissolved in the mixed solvent of EC and DEC of 1L (volume ratio 1: 1).Positive pole, negative pole, electrolyte are assembled into simulated battery in the glove box of argon shield.The testing procedure of simulated battery: at first the electric current with C/2 discharges and recharges between 2-4.2V, and the capacity of being emitted is the discharge capacity under this multiplying power; Circulate after several weeks, progressively improve the current density that discharges and recharges, up to 10C.The test result of simulated battery is listed in table 1.
Result according to table 1 can find out; The composite material (for example embodiment 35) that coats boracic carboritride of the present invention is under the high magnification of 5C and 10C; Battery performance is greatly improved; Specific capacity respectively can be 149mAh/g and 135mAh/g (capability retention is respectively 93% and 84%), the material of other carbon nitrogen or the coating of boron carbon under the high magnification of 5C and 10C, battery performance also be greatly improved (referring to table 1); And the sample that only has carbon to coat, its specific capacity is respectively 132mAh/g and 121mAh/g.Like embodiment 35, the battery of the sample assembling after the boron carboritride coats is grown circulation under the 1C multiplying power, and after 800 weeks of circulation, the conservation rate of specific capacity is 92%.This shows that the boron carboritride coats and greatly improved LiFePO 4Conductivity, its high rate performance and long cyclical stability all are greatly improved.The performance of clad material that the cladding ratio that contains carboritride or boron carbon compound or boron carboritride only contains carbon is excellent more.
The composition of table 1 composite material and the test result of simulated battery
Figure BSA00000196557600131
Figure BSA00000196557600151

Claims (10)

1. polyanion composite material, this composite material has following general formula: B xC yN z-L aD ' bM cD " dXO eA f,
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is selected from a kind of among Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta and the W;
M is selected from a kind of among Fe, Mn, Co, Ni, Ti and the V;
D " is selected from a kind of among Li, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La and the Ce;
X is selected from a kind of among P, Si, S, B and the C;
A is selected from a kind of among N and the F;
And D ', M and D " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously.
2. composite material according to claim 1 is characterized in that, said B xC yN zBe coated on Li aD ' bM cD " dXO eA fThe surface of material granule.
3. composite material according to claim 1 and 2 is characterized in that, said B xC yN zWeight percentage in said composite material is 0.1%-20%, is preferably 1%-10%.
4. according to each described composite material in the claim 1 to 3, it is characterized in that, when x=0, said B xC yN zThe weight percentage of middle nitrogen is 0.001%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0.0001%-10%, is preferably 0.01%-3%; When x ≠ 0, said B xC yN zThe weight percentage of middle nitrogen is 0%-50%, is preferably 0.01%-30%; The weight percentage of nitrogen in said composite material is 0%-10%, is preferably 0.01%-3%.
5. according to each described composite material in the claim 1 to 4, it is characterized in that, when z=0, said B xC yN zThe weight percentage of middle boron is 0.001%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0.0001%-6%, is preferably 0.01%-1%; When z ≠ 0, said B xC yN zThe weight percentage of middle boron is 0%-30%, is preferably 0.01%-10%; The weight percentage of boron in said composite material is 0%-10%, is preferably 0.01%-1%.
6. the preparation method of each described composite material in the claim 1 to 5, this preparation method is selected from coating method or mechanical ball milling method.
7. preparation method according to claim 6 is characterized in that, said coating method comprises the steps:
(1) with L aD ' bM cD " dXO eA fWith the ionic liquid that contains boron carbon or carbon nitrogen or boron carbon nitrogen, for example [EMIm] [N (CN) 2] or other organic compound in blender, mixed 5-30 minute, obtain the mixture of the two
Wherein, B xC yN zFor containing boron carbon or carbon nitrogen or boron carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
D ' is selected from a kind of among Na, Mg, Al, Si, K, Ca, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Ag, In, Sn, La, Ce, Ta and the W;
M is selected from a kind of among Fe, Mn, Co, Ni, Ti and the V;
D " is selected from a kind of among Li, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In, Sn, Ta, W, La and the Ce;
X is selected from a kind of among P, Si, S, B and the C;
A is selected from a kind of among N and the F;
And D ', M and D " are not a kind of element simultaneously;
X, y, z, a, b, c, d, e, f represents molar percentage, 0≤x＜1,0＜y＜1,0≤z＜1,0＜a≤2,0≤b＜1,0＜c≤1,0≤d＜1,3≤e≤4,0≤f≤1, and x and z are not 0 simultaneously; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) obtains is warming up to 600 ℃ from room temperature, and under this temperature, kept 2 hours with 2 ℃/minute speed, make the abundant cracking of ionic liquid, obtain said composite material after the cooling.
8. each described composite material is preparing electrode material of lithium battery, the for example purposes in the positive electrode in the claim 1 to 5.
9. positive pole, this positive pole comprise collector and load on the positive electrode on this collector, it is characterized in that said positive electrode contains each described composite material in the claim 1 to 5.
10. lithium battery, this battery comprises positive pole, negative pole and electrolyte, it is characterized in that, said positive pole comprises the described positive pole of claim 9.
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