CN102315440A - Spinel composite material, preparation method and application thereof - Google Patents
Spinel composite material, preparation method and application thereof Download PDFInfo
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- CN102315440A CN102315440A CN201010228697XA CN201010228697A CN102315440A CN 102315440 A CN102315440 A CN 102315440A CN 201010228697X A CN201010228697X A CN 201010228697XA CN 201010228697 A CN201010228697 A CN 201010228697A CN 102315440 A CN102315440 A CN 102315440A
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Abstract
The invention relates to a spinel composite material, a preparation method and application thereof. The composite material provided by the invention has a general formula of CxNy-(LaM'b)4(McM''d)5O12-eAf, wherein the CxNy is a compound containing carbon and nitrogen. The invention also provides a preparation method and application of the composite material. The invention also provides a cathode comprising the composite material of the invention, and a lithium battery and an electrochemical supercapacitor comprising the cathode. The composition material of the invention has high electronic conductivity and ionic conductivity, particularly high multiplying performance and high cyclical stability.
Description
Technical field
The present invention relates to a kind of spinelle composite material, particularly, the present invention relates to a kind of spinelle composite material that contains 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 present commercially available battery is mainly LiCoO
2, LiMn
2O
4Deng, negative material is mainly the graphite-like material with carbon element.In recent years, spinelle Li
4Ti
5O
12As negative material, caused the great interest of people with its safe voltage range, excellent cycle performance.Yet, because Li
4Ti
5O
12Itself be insulator, electronic conductivity is low, and the capacity of battery is far below its theoretical capacity when high current charge-discharge.
In order to address this 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 Mg
2+, Cr
3+The doping of ion; 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.For example ZaghibK people such as (2003) discloses spinelle Li
4Ti
5O
12The method of coated with carbon (with reference to Guerfi A, Sevigny S, Lagace M, Hovington P; Kinoshita K, Zaghib K, JOURNAL OFPOWER SOURCES; 2003,119,88-94); Improve the electronics contact between the particle, improved the electronic conductivity of material, greatly improved Li
4Ti
5O
12Chemical property.
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 conductivity and ionic conductivity 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 Li
4Ti
5O
12Electronic conductivity and the ionic conductivity of spinels material during as serondary lithium battery and electrochemical super-capacitor electrode material is low; Adopt present existing technical method can not improve the shortcoming of the high rate performance and the cycle performance of material simultaneously; The present invention provides a kind of spinelle composite material, and the high conductive compound that this composite material contains carbon nitrogen through introducing has significantly improved the high rate performance and the cycle performance of material.Negative 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:
The invention provides a kind of spinelle composite material, this composite material has following general formula:
C
xN
y-(L
aM′
b)
4(M
cM″
d)
5O
12-eA
f，
Wherein, C
xN
yFor containing the carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
X, y, a, b, c, d, e and f are molar percentage, and 0＜x＜1,0＜y＜1,0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4.
In the above-mentioned composite material, the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial the surface or with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial mixes mutually, preferably, and the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material.
In the above-mentioned composite material, the said carbon nitrogen compound C that contains
xN
yWeight percentage in said composite material is 0.1%-20%, is preferably 3%-10%.
In the above-mentioned composite material, the said carbon nitrogen compound C that contains
xN
yThe weight percentage of middle nitrogen is 0.0001%-50%, is preferably 0.01%-30%; The weight percentage of N in said composite material is 0.00001%-10%, is preferably 0.03%-3%.
The present invention also provides the preparation method of above-mentioned composite material, and this preparation method is selected from a kind of in coating method, mechanical ball milling method and the direct mixing method.
Wherein, said coating method comprises the steps:
(1) with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
f, Li for example
4Ti
5O
12Contain the organic substance of carbon nitrogen, for example [EMIm] [N (CN) with the ionic liquid that contains carbon nitrogen or other
2] be to mix 10-20 minute in the blender of 2000rpm-2800rpm at rotating speed, obtain the mixture of the two,
Wherein, L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
A, b, c, d, e and f are molar percentage, and 0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) is obtained with 2 ℃/minute speed, and kept 2 hours under this temperature from being warming up to 600 ℃ from room temperature, made the abundant cracking of ionic liquid, obtained said composite material after the cooling.
The present invention also provides the application of above-mentioned composite material in preparation lithium battery and electrochemical super-capacitor electrode material.
The present invention also provides a kind of negative pole, and this negative pole comprises collector and load on the negative material on this collector that said negative material 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, and said negative pole is the above-mentioned negative 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 spinelle composite material, and this composite material has following general formula:
C
xN
y-(L
aM′
b)
4(M
cM″
d)
5O
12-eA
f，
Wherein, C
xN
yFor containing the carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably, L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
X, y, a, b, c, d, e and f are molar percentage, and 0＜x＜1,0＜y＜1,0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4.
According to the present invention, C
xN
yFor containing carbon nitrogen compound, (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fBe active electrode material, be preferably (Li
aM '
b)
4(Ti
cM "
d)
5O
12-eA
f), Li more preferably
4Ti
5O
12The present invention contains the high conductive compound of carbon nitrogen through interpolation, can improve the electronic conductivity of negative material on the one hand; Can reduce on the other hand lithium ion its active material with contain carbon nitrogen compound migration activation energy at the interface, thereby improve lithium ion at the interface ionic conductivity, improved the high rate performance of negative material.
In the present invention, the said carbon nitrogen compound C that contains
xN
yCan be coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material also can be directly and (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial mixes mutually, preferably, and the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material.The present invention will contain the carbon nitrogen compound and be coated on the active electrode material surface, improve interface stability, and then improve the cycle life of negative material.
In the present invention, the said carbon nitrogen compound C that contains
xN
yWeight percentage in said negative material is 0.1%-20%, is preferably 3%-10%.
In the present invention, the said carbon nitrogen compound C that contains
xN
yThe weight percentage of middle nitrogen is 0.0001%-50%, is preferably 0.01%-30%; The weight percentage of N in said composite material is 0.00001%-10%, is preferably 0.03%-3%.
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 active electrode material (L
aM '
b)
4(M
cM "
d)
5O
12-eA
f, Li for example
4Ti
5O
12Contain the organic substance of carbon nitrogen, for example [EMIm] [N (CN) with the ionic liquid that contains carbon nitrogen or other
2] be to mix 10-20 minute in the blender of 2000rpm-2800rpm at rotating speed, obtain the mixture of the two,
Wherein, L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
A, b, c, d, e and f are molar percentage, and 0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) is obtained with 2 ℃/minute speed, and kept 2 hours under this temperature from being warming up to 600 ℃ from room temperature, made the abundant cracking of ionic liquid, obtained 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 Li
4Ti
5O
12, be put in the centrifuge tube, in required ratio, get the ionic liquid that contains carbon nitrogen, for example [EMIm] [N (CN)
2]; The adding powder is placed in the turbine mixer that rotating speed is 2000rpm-2800rpm and vibrated 10 to 20 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 nitrogen or the argon gas atmosphere, said mixture is 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, 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, be total to knowledge like this area, and those of ordinary skills also can adopt other preparation methods, for example mechanical ball milling method, direct mixing method (carbon containing nitrogen compound C soon
xN
yWith active electrode material (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fDirectly mix by a certain percentage) wait and prepare above-mentioned composite material of the present invention.
The present invention also provides above-mentioned composite material in preparation serondary lithium battery and electrochemical super-capacitor electrode material, to be used to make negative pole or anodal purposes; Described negative pole comprises collector and loads on the negative material on this collector that said negative material contains above-mentioned composite material.Because the present invention only relates to the improvement to composite material, the preparation method of anticathode and the composition of negative pole are not special to be limited, and adopts the conventional preparation method in this area to get final product with forming.Described collector can adopt all available negative current collectors 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, and said negative pole is the above-mentioned negative pole that contains composite material of the present invention.
Particularly, the present invention can process secondary lithium battery cathode with the negative material that contains carboritride, forms serondary lithium battery with positive pole, the electrolyte of routine.The conductive additive that uses in the negative pole can be carbon, conducting metal oxide or the metal of routine use; The anodal active material that uses can comprise LiMn
2O
4, LiNi
0.5Mn
1.5O
4And Li
1+zM
1-zO
2(wherein, M is one or more transition metals, z＞0) etc.; 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 the spinelle composite material that contains carboritride of the present invention to be applicable to that as the serondary lithium battery of electrode 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 for example Li
4Ti
5O
12Introduce the high conductive compound that contains carbon nitrogen in the spinels active electrode material, can improve the electronic conductivity of negative material on the one hand; Can reduce on the other hand lithium ion its active material with contain carbon nitrogen compound migration activation energy at the interface, thereby improve lithium ion at the interface ionic conductivity, improved the high rate performance of negative material.
2, the present invention will contain the carbon nitrogen compound and be coated on for example Li
4Ti
5O
12Interface stability has also been improved on the surface of spinels active electrode material particle simultaneously, and then has improved the cycle life of negative material.
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 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 that contains carboritride of the present invention good, the lithium battery of preparation, its high rate performance all is greatly improved with long cyclical stability, sees the explanation of table 4.
Description of drawings
Below with reference to accompanying drawing embodiment of the present invention are described, wherein:
Fig. 1 is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 165 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Charging and discharging curve under the different electric current density;
Fig. 2 is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 495 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Charging and discharging curve under the different electric current density;
Fig. 3 is for using ionic liquid [BMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Charging and discharging curve under the different electric current density;
Fig. 4 a is used original porous Li
4Ti
5O
12Photo;
Fig. 4 b is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12The photo of powder;
Fig. 5 a is used original porous Li
4Ti
5O
12ESEM (SEM) figure;
Fig. 5 b is with 1g porous Li when using ionic liquid [EMIm] [N (CN) 2] as carbon nitrogen source
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Sem photograph;
Fig. 6 a is used original porous Li
4Ti
5O
12X-ray diffraction (XRD) figure;
Fig. 6 b is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12X-ray diffractogram;
Fig. 7 is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Transmission electron microscope (HRTEM) figure;
Fig. 8 a is used original porous Li
4Ti
5O
12Raman spectrogram;
Fig. 8 b is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Raman spectrogram;
Fig. 9 a is used original porous Li
4Ti
5O
12The x-ray photoelectron power spectrum (XPS) of N1s track;
Fig. 9 b is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12The x-ray photoelectron power spectrum of N1s track;
Dotted line is original porous Li among Figure 10
4Ti
5O
12Charging and discharging curve under the different electric current density; Solid line is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Charging and discharging curve under the different electric current density;
Figure 11 is for using ionic liquid [EMIm] [N (CN)
2] during as carbon nitrogen source with 1g porous Li
4Ti
5O
12Add 320 μ L ionic liquid ratios and carry out the Li after 600 ℃ of heat treatments coat
4Ti
5O
12Preceding 1000 all charging and discharging capacities under the 2C current density;
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention., these embodiment are not used in restriction scope of the present invention but only limiting to the present invention is described.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
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
Under dry atmosphere, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g porous Li
4Ti
5O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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 percentage by weight of nitrogen in CxNy is about 30%, and the percentage by weight of CxNy in composite material is about 6%.
Embodiment 2-3
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the 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 ionic liquid and content of active substance are different, obtain the composite material of different CxNy percentage by weights, are respectively about 3% and 10%.
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, and its charging and discharging curve is listed in Fig. 1 and Fig. 2 respectively.
Embodiment 4-5
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the 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 heat treatment temperature is different, obtains the composite material of the percentage by weight of different nitrogen in CxNy, is respectively about 40% and 8%.
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 6-9
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the 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 ionic liquid of being selected for use is different, obtains the composite material of different CxNy percentage by weights.
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, and wherein, the charging and discharging curve of embodiment 6 is listed in Fig. 3.
This embodiment is used to explain composite material provided by the invention and preparation method thereof (direct mixing method).
The CxNy compound and the Li that directly will contain carbon nitrogen
4Ti
5O
12Mix the composite material that contains CxNy that obtains by 6%: 94% weight ratio.
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 11
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the 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 the Li that is selected for use
4Ti
5O
12The pattern of powder is nanometer rods or nano wire, the composite material that contains CxNy that obtains.
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 12
This embodiment is used to explain composite material provided by the invention and preparation method thereof (mechanical ball milling method).
CxNy-Li
4Ti
5O
12Composite material can also be synthetic through following steps.At first, take by weighing Li at 1: 2.5 according to mol ratio
2CO
3And TiO
2, 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 Li
4Ti
5O
12: 400 microlitre ionic liquids), at high-purity Ar gas or N
2Heat-treat under the protective atmosphere of gas, heat treatment temperature is 800 ℃, and this temperature constant temperature is 10 hours again, and natural cooling then obtains containing the composite material of CxNy.
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.
Table 1
Annotate: active electrode material is Li in the table 1
4Ti
5O
12
Embodiment 13
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
3.9Mg
0.1Ti
5O
12, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
3.9Mg
0.1Ti
5O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 14
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Ti
4.85Al
0.15O
12, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Ti
4.85Al
0.15O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 15
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Ti
4.8Mo
0.2O
12, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Ti
4.8Mo
0.2O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 16
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Ti
5O
11.995, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Ti
5O
11.995Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 17
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Ti
5O
11.9F
0.05, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Ti
5O
11.9F
0.05Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 18
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Ti
5O
11.8N
0.06, with 320 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Ti
5O
11.8N
0.06Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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.
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 2.
Embodiment 19
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Mn
5O
12, with 150 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Mn
5O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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 450 ℃ from room temperature with the speed of 2 ℃/min, kept 2 hours at 450 ℃, make the abundant cracking of ionic liquid, treat that tube furnace cooling back takes out sample, 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 2.
This embodiment is used to explain composite material provided by the invention and preparation method thereof (coating method).
By the composite material that is used for serondary lithium battery of the present invention that the method preparation of embodiment 1 is formed by table 2, different is that the active material of selecting for use is Li
4Mn
4.85Mo
0.15O
12, with 150 μ L ionic liquid [EMIm] [N (CN)
2] adding 1g Li
4Mn
4.85Mo
0.15O
12Powder, vibration is 10 minutes in the turbine mixer of 2000rpm, obtains white 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 450 ℃ from room temperature with the speed of 2 ℃/min, kept 2 hours at 450 ℃, make the abundant cracking of ionic liquid, treat that tube furnace cooling back takes out sample, 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 2.
Table 2
| 15 | Li 4Ti 4.8Mo 0.2O 12 | 600 | 159 | 144 | 134 | 90.3 |
| 16 | Li 4Ti 5O 11.995 | 600 | 161 | 143 | 133 | 88.8 |
| 17 | Li 4Ti 5O 11.9F 0.05 | 600 | 161 | 147 | 139 | 87.8 |
| 18 | Li 4Ti 5O 11.8N 0.06 | 600 | 160 | 145 | 137 | 88.2 |
| 19 | Li 4Mn 5O 12 | 450 | 151 | 130 | 121 | 71.5 |
| 20 | Li 4Mn 4.85Mo 0.15O 12 | 450 | 149 | 134 | 126 | 72.2 |
Annotate: carbon nitrogen source is ionic liquid [EMIm] [N (CN) in the table 2
2].
The comparative example 1Porous Li before and after embodiment 1 coats
4Ti
5O
12Performance comparison research
Porous Li before and after embodiment 1 coats
4Ti
5O
12Shown in Fig. 4 a and Fig. 4 b.Through SEM, the pattern before and after relatively coating is found to coat the back pattern and is not changed, shown in Fig. 5 a and Fig. 5 b; The result of XRD and HRTEM can know that the crystal structure of sample does not change, and is spinel structure, like Fig. 6 a, Fig. 6 b and shown in Figure 7; Can find out that from the result of Raman and XPS the surface has exist (like Fig. 8 a, Fig. 8 b, Fig. 9 a and Fig. 9 b) of nitrogen, carbon really, the percentage by weight of nitrogen in CxNy is about 30%.Thermogravimetric analysis (TG) is the result show, the percentage by weight of CxNy in composite material is about 6%.
In order to study the chemical property that coats the front and back sample, with the sample making simulated battery.In the lithium titanate before and after coating: acetylene black: the ratio of PVdF binding agent=8: 1: 1 is mixed the formation slurry at normal temperatures and pressures; Evenly be coated on the substrate that aluminium foil is a collector and make electrode slice; The film thickness of gained is the 2-20 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 DMC 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 1-2.2V, 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 3.
Table 3
The result finds than under the low range; The specific capacity of the sample after the coating is more lower slightly than primary sample; This is owing to comprised into the quality of carbon nitrogen coating during the calculated activity material mass, but under the high magnification of 5C and 10C, battery performance is greatly improved; Specific capacity is respectively 145mAh/g and 130mAh/g (capability retention is respectively 90% and 81%), and is merely 60mAh/g and 15mAh/g (capability retention is respectively 35% and 9%) before coating.Sample charging curve under the high magnification of 5C and 10C can not keep platform before coating, and the sample after coating has still kept charging platform (shown in figure 10).The battery of the sample assembling after the coating is grown circulation under the 2C multiplying power, after 1000 weeks of circulation, specific capacity decays to 132.0mAh/g by 150.4mAh/g, and capability retention is 88.1% (shown in figure 11).
The comparative example 2The contrast of the chemical property of the composite material of the sample of carbon containing and embodiment 1
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 6%.
With the sample making simulated battery.In the lithium titanate before and after coating: acetylene black: the ratio of PVdF binding agent=8: 1: 1 is mixed the formation slurry at normal temperatures and pressures; Evenly be coated on the substrate that aluminium foil is a collector and make electrode slice; The film thickness of gained is the 2-20 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 DMC 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 1-2.2V, 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 4.
Table 4
The result finds to coat the composite material that contains carboritride of the present invention under the high magnification of 5C and 10C; Battery performance is greatly improved; Specific capacity is respectively 145mAh/g and 130mAh/g (capability retention is respectively 90% and 81%); And the sample that only has carbon to coat, its specific capacity is respectively 130mAh/g and 116mAh/g (capability retention is respectively 81% and 72%).This shows that carboritride coats the conductivity of greatly having improved lithium titanate, its high rate performance and long cyclical stability all are greatly improved.
Claims (9)
1. spinelle composite material, this composite material has following general formula:
C
xN
y-(L
aM′
b)
4(M
cM″
d)
5O
12-eA
f，
Wherein, C
xN
yFor containing the carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
X, y, a, b, c, d, e and f are molar percentage, and 0＜x＜1,0＜y＜1,0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4.
2. composite material according to claim 1 is characterized in that, the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial the surface or with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial mixes mutually, preferably, and the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material.
3. composite material according to claim 1 and 2 is characterized in that, the said carbon nitrogen compound C that contains
xN
yWeight percentage in said composite material is 0.1%-20%, is preferably 3%-10%.
4. according to each described composite material in the claim 1 to 3, it is characterized in that the said carbon nitrogen compound C that contains
xN
yThe weight percentage of middle nitrogen is 0.0001%-50%, is preferably 0.01%-30%; The weight percentage of N in said composite material is 0.00001%-10%, is preferably 0.03%-3%.
5. the preparation method of each described composite material in the claim 1 to 4, this preparation method are selected from a kind of in coating method, mechanical ball milling method and the direct mixing method.
6. method according to claim 5, said coating method comprises the steps:
(1) with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
f, Li for example
4Ti
5O
12Contain the organic substance of carbon nitrogen, for example [EMIm] [N (CN) with the ionic liquid that contains carbon nitrogen or other
2] be to mix 10-20 minute in the blender of 2000rpm-2800rpm at rotating speed, obtain the mixture of the two,
Wherein, L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
A, b, c, d, e and f are molar percentage, and 0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4; And
(2) at tube furnace, in nitrogen or the argon gas atmosphere, the mixture that step (1) is obtained with 2 ℃/minute speed, and kept 2 hours under this temperature from being warming up to 600 ℃ from room temperature, made the abundant cracking of ionic liquid, obtained said composite material after the cooling.
7. the purposes of each described composite material in preparation lithium battery and electrochemical super-capacitor electrode material in the claim 1 to 4.
8. negative pole, this negative pole comprise collector and load on the negative material on this collector, it is characterized in that said negative material contains the composite material with following general formula:
C
xN
y-(L
aM′
b)
4(M
cM″
d)
5O
12-eA
f，
Wherein, C
xN
yFor containing the carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
X, y, a, b, c, d, e and f are molar percentage, and 0＜x＜1,0＜y＜1,0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4;
Preferably, the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial the surface or with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial mixes mutually, preferably, and the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material;
Preferably, the said carbon nitrogen compound C that contains
xN
yWeight percentage in said composite material is 0.1%-20%, is preferably 3%-10%;
Preferably, the said carbon nitrogen compound C that contains
xN
yThe weight percentage of middle nitrogen is 0.0001%-50%, is preferably 0.01%-30%; The weight percentage of N in said composite material is 0.00001%-10%, is preferably 0.03%-3%.
9. lithium battery, this battery comprises positive pole, negative pole and electrolyte, it is characterized in that, said negative pole comprises collector and loads on the negative material on this collector that said negative material contains the composite material with following general formula:
C
xN
y-(L
aM′
b)
4(M
cM″
d)
5O
12-eA
f，
Wherein, C
xN
yFor containing the carbon nitrogen compound;
L is selected from a kind of among Li and the Na, and preferably L is Li;
M ' 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, W, La and the Ce;
M is selected from a kind of among Ti, Mn and the Mo;
M " 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;
A is selected from a kind of among N, F, P and the S;
M and M " are not a kind of element simultaneously;
X, y, a, b, c, d, e and f are molar percentage, and 0＜x＜1,0＜y＜1,0＜a≤1,0≤b＜1,0＜c≤1,0≤d＜1,0≤e＜4,0≤f＜4;
Preferably, the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial the surface or with (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fMaterial mixes mutually, preferably, and the said carbon nitrogen compound C that contains
xN
yBe coated on (L
aM '
b)
4(M
cM "
d)
5O
12-eA
fThe surface of material;
Preferably, the said carbon nitrogen compound C that contains
xN
yWeight percentage in said composite material is 0.1%-20%, is preferably 3%-10%;
Preferably, the said carbon nitrogen compound C that contains
xN
yThe weight percentage of middle nitrogen is 0.0001%-50%, is preferably 0.01%-30%; The weight percentage of N in said composite material is 0.00001%-10%, is preferably 0.03%-3%.
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| CN103337631A (en) * | 2013-07-04 | 2013-10-02 | 哈尔滨工程大学 | Carbon-nitrogen co-coating method for improving high rate discharge performance of lithium titanate and inhibiting gas generation |
| CN104409714A (en) * | 2014-11-21 | 2015-03-11 | 湖南文理学院 | Method for preparing nitrogen-carbon co-coated lithium titanate anode material |
| CN104617291A (en) * | 2015-01-24 | 2015-05-13 | 复旦大学 | Uniform carbon coated lithium ion battery anode/cathode material and preparation method thereof |
| CN105244181A (en) * | 2015-08-24 | 2016-01-13 | 太原理工大学 | Spinel type metal oxide of high specific capacitance and preparation and application of metal oxide |
| WO2017101470A1 (en) * | 2015-12-18 | 2017-06-22 | 华为技术有限公司 | Negative electrode active material of lithium ion secondary battery and preparation method therefor, negative electrode plate of lithium ion secondary battery, and lithium ion secondary battery |
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| CN103337631A (en) * | 2013-07-04 | 2013-10-02 | 哈尔滨工程大学 | Carbon-nitrogen co-coating method for improving high rate discharge performance of lithium titanate and inhibiting gas generation |
| CN103337631B (en) * | 2013-07-04 | 2015-08-12 | 哈尔滨工程大学 | Improve lithium titanate high-rate discharge ability and suppress the carbon nitrogen of aerogenesis to be total to method for coating |
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| CN104409714A (en) * | 2014-11-21 | 2015-03-11 | 湖南文理学院 | Method for preparing nitrogen-carbon co-coated lithium titanate anode material |
| CN104617291A (en) * | 2015-01-24 | 2015-05-13 | 复旦大学 | Uniform carbon coated lithium ion battery anode/cathode material and preparation method thereof |
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| CN106898738A (en) * | 2015-12-18 | 2017-06-27 | 华为技术有限公司 | A kind of negative electrode of lithium ionic secondary battery and preparation method, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
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| CN106898738B (en) * | 2015-12-18 | 2019-07-23 | 华为技术有限公司 | A kind of negative electrode of lithium ionic secondary battery and preparation method, cathode pole piece of lithium ion secondary battery and lithium ion secondary battery |
| US11569496B2 (en) | 2015-12-18 | 2023-01-31 | Huawei Technologies Co., Ltd. | Lithium-ion rechargeable battery negative electrode active material and preparation method thereof, lithium-ion rechargeable battery negative electrode plate, and lithium-ion rechargeable battery |
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Application publication date: 20120111 |