CN103553015B - The preparation method of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery - Google Patents
The preparation method of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery Download PDFInfo
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- CN103553015B CN103553015B CN201310454985.0A CN201310454985A CN103553015B CN 103553015 B CN103553015 B CN 103553015B CN 201310454985 A CN201310454985 A CN 201310454985A CN 103553015 B CN103553015 B CN 103553015B
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Abstract
The present invention relates to a kind of preparation method of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery, comprise: lithium salts, ferrous salt and the material dissolution containing phosphate anion in anhydrous lower alcohol, are obtained the anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion by (1); (2) carbon nanotube is joined in the above-mentioned anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion, through ultrasonic and obtain uniform mixture after stirring; (3) crucible filling said mixture is put into encloses container top, the bottom of described encloses container is placed with proper ammonia in advance, and described mixture does not directly contact with ammoniacal liquor, encloses container is heated to 150 ~ 250 DEG C, and is incubated 1 ~ 72 hour; Finally will obtain powder washing, drying, to obtain final product.The carbon nano tube modified ferrous phosphate doping lithium anode material well-crystallized that the present invention prepares, carbon nano tube modified layer thickness are controlled; And preparation process is without the need to calcination processing, energy-conserving and environment-protective.
Description
Technical field
The invention belongs to the preparation field of anode material for lithium-ion batteries, particularly a kind of preparation method of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery.
Background technology
Lithium ion battery because its open circuit voltage is high, have extended cycle life, energy density is high, self-discharge is low, memory-less effect and the advantage such as environmentally friendly, occurs that beginning has just captured the Battery Market of mobile phone and other portable digital product with surprising rapidity from it.But how improving its energy density, power density and high rate charge-discharge performance is further one of difficult problem being applied to electromobile field by its mass-producing always.And in lithium ion battery, the performance of positive electrode material determines the key factor of lithium ion battery chemical property, safety performance and Costco Wholesale often.
In current existing positive electrode material, LiFePO 4 (LiFePO
4) because safety performance is good, have extended cycle life, raw material sources extensively, the advantage such as non-environmental-pollution, (J.Electrochem.Soc. is taught from J.B.Goodenough in 1997,1997,144,1188-1194) be just the focus of anode material for lithium-ion batteries research and development since its reversible embedding lithium-Tuo lithium characteristic of Late Cambrian always.But through years of researches, it also also exists some application problems, wherein topmost is exactly rate charge-discharge poor performance, and the key factor affecting LiFePO 4 high rate performance is exactly low electronic conductivity and the Li of material
+mobility, is only 10
-9s/cm.The improvement generally adopted in recent years its low electronic conductivity and Li
+the method of mobility is to improve ion transport at its Surface coating electronics good conductor or fast-ionic conductor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery, the positive electrode material well-crystallized that the method obtains, carbon nano tube modified layer thickness are controlled, and preparation process is without the need to calcination processing, energy-conserving and environment-protective.
The preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery of the present invention, comprising:
(1) by lithium salts, ferrous salt and containing the material dissolution of phosphate anion in anhydrous lower alcohol, obtain the anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion, wherein the concentration of various ion is respectively lithium ion 0.005 ~ 1.0mol/L, ferrous ion 0.001 ~ 0.2mol/L, phosphate anion 0.005 ~ 0.3mol/L;
(2) carbon nanotube is joined in the above-mentioned anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion, through ultrasonic and obtain uniform mixture after stirring;
(3) crucible filling said mixture is put into encloses container top, the bottom of described encloses container is placed with proper ammonia in advance, and described mixture does not directly contact with ammoniacal liquor, encloses container is heated to 150 ~ 250 DEG C, and is incubated 1 ~ 72 hour; Finally will obtain powder washing, drying, obtain carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery.
In described step (1), lithium salts is one or more in lithium chloride, lithium nitrate, Lithium Acetate.
In described step (1), ferrous salt is one or both in iron protochloride, Iron nitrate.
Be one or both in phosphoric acid, Ureaphil containing the raw material of phosphate anion in described step (1).
In described step (1), anhydrous lower alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol.
In described step (2), the consumption of carbon nanotube is 0.01 ~ 10.0mg/L.
In described step (3), ammonia concn is 0.004 ~ 0.8mol/L.
In described step (3), the consumption of ammoniacal liquor is 1 ~ 2000 with the ratio of the amount of substance of lithium ion.
Beneficial effect:
The present invention utilizes carbon nanotube to improve the lower electronic conductivity of LiFePO 4 and Li
+mobility, the carbon nano tube modified ferrous phosphate doping lithium anode material well-crystallized that the present invention prepares, carbon nano tube modified layer thickness are controlled; And preparation process is without the need to calcination processing, energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 is the standard diffraction collection of illustrative plates of ferrousphosphate lithium material, the X-ray diffraction result of the carbon nano tube modified ferrous phosphate doping lithium anode material (b) prepared in the carbon nano tube modified ferrous phosphate doping lithium anode material (a) prepared in embodiment 1 and embodiment 2.
Fig. 2 is the stereoscan photograph of the carbon nano tube modified ferrous phosphate doping lithium anode material prepared in embodiment 1.
Fig. 3 is the stereoscan photograph of the carbon nano tube modified ferrous phosphate doping lithium anode material prepared in embodiment 2.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
0.1g lithium chloride, 0.16g tetra-water iron protochloride, 72 μ L phosphoric acid are joined in 8mL dehydrated alcohol, stir 2 minutes, 6mg carbon nanotube is added in above-mentioned anhydrous alcohol solution, ultrasonic and stir each 3 minutes.The anhydrous alcohol solution of carbon nanotubes is poured in crucible, then crucible is placed in the top of sealable container.Sealable container bottom is placed with 3mL ammoniacal liquor (0.05mol/L) in advance.After container closure, put into baking oven, start to be heated to 200 DEG C, temperature rise rate is 10 ~ 20 DEG C/min, and temperature is incubated 10 hours after reaching the temperature of setting.Naturally cool to room temperature after insulation terminates, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 DEG C of vacuum dryings 8 hours.
The X-ray diffraction result of the carbon nano tube modified ferrous phosphate doping lithium anode material that Fig. 1 (a) prepares under giving this kind of condition.As can be observed from Figure, the position of its diffraction peak conforms to completely with the position of standard card (PDF#41-1376), but because the amount of carbon nanotube is little, its diffraction peak has overlapping with the position of LiFePO 4 diffraction peak again, so do not observe the diffraction peak of carbon nanotube.
The stereoscan photograph of the carbon nano tube modified ferrous phosphate doping lithium anode material that Fig. 2 prepares under giving this kind of condition, can see that carbon nanotube has been coated on the surface of LiFePO 4.
Embodiment 2
0.1g lithium chloride, 0.16g tetra-water iron protochloride, 72 μ L phosphoric acid are joined in 8mL dehydrated alcohol, stir 2 minutes, 12mg carbon nanotube is added in above-mentioned anhydrous alcohol solution, ultrasonic and stir each 3 minutes.The anhydrous alcohol solution of carbon nanotubes is poured in crucible, then crucible is placed in the top of sealable container.Sealable container bottom is placed with 3mL ammoniacal liquor (0.05mol/L) in advance.After container closure, put into baking oven, start to be heated to 200 DEG C, temperature rise rate is 10 ~ 20 DEG C/min, and temperature is incubated 10 hours after reaching the temperature of setting.Naturally cool to room temperature after insulation terminates, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 DEG C of vacuum dryings 8 hours.
The X-ray diffraction result of the carbon nano tube modified ferrous phosphate doping lithium anode material that Fig. 1 (b) prepares under giving this kind of condition.As we can see from the figure, the position of its diffraction peak conforms to completely with the position of standard card (PDF#41-1376), but its diffraction peak has overlapping with the position of LiFePO 4 diffraction peak, so do not observe the diffraction peak of carbon nanotube.
The stereoscan photograph of the carbon nano tube modified ferrous phosphate doping lithium anode material that Fig. 3 prepares under giving this kind of condition, can see that carbon nanotube has been coated on the surface of LiFePO 4 and thicker.
Embodiment 3
0.1g lithium chloride, 0.16g tetra-water iron protochloride, 72 μ L phosphoric acid are joined in 8mL dehydrated alcohol, stir 2 minutes, 6mg carbon nanotube is added in above-mentioned anhydrous alcohol solution, ultrasonic and stir each 3 minutes.The anhydrous alcohol solution of carbon nanotubes is poured in crucible, then crucible is placed in the top of sealable container.Sealable container bottom is placed with 3mL ammoniacal liquor (0.1mol/L) in advance.After container closure, put into baking oven, start to be heated to 170 DEG C, temperature rise rate is 10 ~ 20 DEG C/min, and temperature is incubated 24 hours after reaching the temperature of setting.Naturally cool to room temperature after insulation terminates, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 DEG C of vacuum dryings 8 hours.
Embodiment 4
0.1g lithium chloride, 0.16g tetra-water iron protochloride, 72 μ L phosphoric acid are joined in 8mL dehydrated alcohol, stir 2 minutes, 12mg carbon nanotube is added in above-mentioned anhydrous alcohol solution, ultrasonic and stir each 3 minutes.The anhydrous alcohol solution of carbon nanotubes is poured in crucible, then crucible is placed in the top of sealable container.Sealable container bottom is placed with 3mL ammoniacal liquor (0.1mol/L) in advance.After container closure, put into baking oven, start to be heated to 170 DEG C, temperature rise rate is 10 ~ 20 DEG C/min, and temperature is incubated 36 hours after reaching the temperature of setting.Naturally cool to room temperature after insulation terminates, open encloses container, take out crucible, pour out powder, respectively wash 3 times with distilled water and raw spirit, through 60 DEG C of vacuum dryings 8 hours.
Claims (8)
1. a preparation method for carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery, comprising:
(1) by lithium salts, ferrous salt and containing the material dissolution of phosphate anion in anhydrous lower alcohol, obtain the anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion, wherein the concentration of various ion is respectively lithium ion 0.005 ~ 1.0mol/L, ferrous ion 0.001 ~ 0.2mol/L, phosphate anion 0.005 ~ 0.3mol/L;
(2) carbon nanotube is joined in the above-mentioned anhydrous alcohol solution containing lithium ion, ferrous ion and phosphate anion, through ultrasonic and obtain uniform mixture after stirring;
(3) crucible filling said mixture is put into encloses container top, the bottom of described encloses container is placed with proper ammonia in advance, and described mixture does not directly contact with ammoniacal liquor, encloses container is heated to 150 ~ 250 DEG C, and is incubated 1 ~ 72 hour; Finally will obtain powder washing, drying, obtain carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery.
2. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (1), lithium salts is one or more in lithium chloride, lithium nitrate, Lithium Acetate.
3. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (1), ferrous salt is one or both in iron protochloride, Iron nitrate.
4. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: be one or both in phosphoric acid, Ureaphil containing the raw material of phosphate anion in described step (1).
5. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (1), anhydrous lower alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol.
6. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (2), the consumption of carbon nanotube is 0.01 ~ 10.0mg/L.
7. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (3), ammonia concn is 0.004 ~ 0.8mol/L.
8. the preparation method of a kind of carbon nano tube modified cathode material of lithium iron phosphate lithium-ion battery according to claim 1, is characterized in that: in described step (3), the consumption of ammoniacal liquor is 1 ~ 2000 with the ratio of the amount of substance of lithium ion.
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Citations (4)
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|---|---|---|---|---|
| CN101519199A (en) * | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | Method for preparing high-density spherical lithium iron phosphate for lithium ion power battery |
| CN101645504A (en) * | 2008-08-07 | 2010-02-10 | 赵兵 | Method for preparing lithium iron phosphate of anode material of lithium ion battery |
| CN102447110A (en) * | 2011-12-14 | 2012-05-09 | 哈尔滨工业大学 | Preparation method of carbon nanomaterial-doped spherical iron phosphate and preparation method of carbon nanomaterial-doped lithium iron phosphate |
| CN103000891A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cathode material Li2MnSiO4/PPY for lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645504A (en) * | 2008-08-07 | 2010-02-10 | 赵兵 | Method for preparing lithium iron phosphate of anode material of lithium ion battery |
| CN101519199A (en) * | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | Method for preparing high-density spherical lithium iron phosphate for lithium ion power battery |
| CN102447110A (en) * | 2011-12-14 | 2012-05-09 | 哈尔滨工业大学 | Preparation method of carbon nanomaterial-doped spherical iron phosphate and preparation method of carbon nanomaterial-doped lithium iron phosphate |
| CN103000891A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cathode material Li2MnSiO4/PPY for lithium ion battery |
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