CN102208619B - Method for preparing magnesium-doped xLiFePO4.yLi3V2(PO4)3 lithium ion battery anode material - Google Patents
Method for preparing magnesium-doped xLiFePO4.yLi3V2(PO4)3 lithium ion battery anode material Download PDFInfo
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- CN102208619B CN102208619B CN2011100981761A CN201110098176A CN102208619B CN 102208619 B CN102208619 B CN 102208619B CN 2011100981761 A CN2011100981761 A CN 2011100981761A CN 201110098176 A CN201110098176 A CN 201110098176A CN 102208619 B CN102208619 B CN 102208619B
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Abstract
The invention discloses a method for preparing a magnesium-doped xLiFePO4.yLi3V2(PO4)3 lithium ion battery anode material, and relates to a method for preparing a lithium ion battery anode material. The method solves the problems of bad existence environment and high cost of prior lithium ion anode materials under the condition that the cycle performance of the lithium ion anode materials is ensured not to reduce. The method comprises the following steps of: weighing lithium source, iron source, vanadium salt, magnesium salt, phosphoric acid source and carbon source, mixing, and performing wet milling, pre-sintering and calcination to obtain the xLiFePO4.yLi3V2(PO4)3. The process is simple. The anode material prepared by the method has good magnification discharge performance; and during 10C discharge, the discharge specific capacity is 90mAh/g, and the capacity is nearly not attenuated after 20 times of cycles.
Description
Technical field
The present invention relates to the preparation method of anode material for lithium-ion batteries.
Background technology
Because lithium ion battery is that energy density is the highest in the present commercialization secondary cell, therefore, be subjected to the great attention that numerous battery of electric vehicle are researched and developed unit.Performance owing to lithium ion battery depends on positive electrode to a great extent again, so the research of anode material for lithium-ion batteries becomes current research focus.
Document (Synthesis and performance of Li
3(V
1-xMg
x)
2(PO
4)
3Cathode materials, " Journal of Power Sources ", on March 6th, 2010, the 5775-5779 page or leaf) anode material for lithium-ion batteries that is made of mutually magnesium doping phosphoric acid vanadium lithium is disclosed, it has the advantage of high power charging-discharging, but friendly inadequately to environment, cost is high too.At present, the method for environmental friendliness and the high problem of cost can be solved, the reduction of the cycle performance of anode material for lithium-ion batteries can be caused again.
XLiFePO
4YLi
3V
2(PO
4)
3It is a kind of novel anode material for lithium-ion batteries.It not only has LiFePO
4Advantage with low cost, but also have Li concurrently
3V
2(PO
4)
3Compound can high power charging-discharging advantage.It is a kind of new material that has potentiality.Some liquid-phase synthesis process of this material have been reported in research before this, but liquid phase preparation process is friendly inadequately to environment.
The present invention adopts carbothermic method to prepare the xLiFePO that magnesium ion mixes
4YLi
3V
2(PO
4)
3Anodal new material has solved existing xLiFePO
4YLi
3V
2(PO
4)
3The problem of the multiplying power discharging property difference of lithium ion battery.
Summary of the invention
The present invention will solve existing lithium ion anode material and have the environment friendly and high problem of cost inadequately under the condition that the cycle performance that guarantees anode material for lithium-ion batteries does not reduce; And provide magnesium doping xLiFePO
4YLi
3V
2(PO
4)
3The preparation method of anode material for lithium-ion batteries.
Magnesium doping xLiFePO in the present embodiment
4YLi
3V
2(PO
4)
3The preparation method of anode material for lithium-ion batteries is undertaken by following step: one, press the Li element, the Fe element, V element, the Mg element, the mol ratio of P element and C element is (x+3y)～1.1 (x+3y): x:2y:0.1 (x+y)～0.5 (x+y): (x+3y): 0.5 (x+3y)～2 (x+3y) ratio takes by weighing the lithium source, source of iron, vanadic salts, magnesium salts, mix after source of phosphoric acid and the carbon source and obtain mixture, then mixture is placed ball mill, carry out wet-milling 2～12h after adding dispersant, namely obtain compound, wherein the volume ratio of dispersant and mixture is 1～10:1, dispersant is absolute ethyl alcohol, acetone or water, 0.05≤x/ (x+y)≤0.95; Two, under the protection of 250～450 ℃ and protection gas, compound presintering 2～6h that step 1 is obtained; Three, the compound after presintering is handled is then calcined 6～30h under the protection of 570～870 ℃ and protection gas, be cooled to room temperature, makes the xLiFePO that magnesium mixes
4YLi
3V
2(PO
4)
3
The magnesium doping xLiFePO that the present invention synthesizes
4YLi
3V
2(PO
4)
3Crystalline particle is even; Charge-discharge test shows, the magnesium doping xLiFePO of preparation
4YLi
3V
2(PO
4)
3Higher first discharge specific capacity and capability retention are arranged, the magnesium doping xLiFePO of preparation
4YLi
3V
2(PO
4)
3The first discharge specific capacity of electrode is 130mAh/g.After 400 circulations, the former is not less than 95% by capability retention.And find this good multiplying power discharging property that just having, and during the 10C discharge, specific discharge capacity is 90mAh/g, 20 times circulation back capacity is decayed hardly; The cyclic voltammetric test shows, synthetic magnesium doping xLiFePO
4YLi
3V
2(PO
4)
3Positive electrode has good invertibity.Technology of the present invention is simple, and cost is low, and the most outstanding advantage is environmental friendliness, has solved environmental pollution problems effectively.
Description of drawings
Fig. 1 is the 7LiFePO of embodiment 12
4Li
3V
2(PO
4)
3The X-ray diffraction spectrogram.Fig. 2 is that embodiment 12 is the synthetic 7LiFePO of carbon source with sucrose
4Li
3V
2(PO
4)
3Discharge curve.Fig. 3 be embodiment 12 with sucrose be carbon source synthetic 7LiFePO
4Li
3V
2(PO
4)
3High rate performance.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: magnesium doping xLiFePO in the present embodiment
4YLi
3V
2(PO
4)
3The preparation method of anode material for lithium-ion batteries is undertaken by following step: one, press the Li element, the Fe element, V element, the Mg element, the mol ratio of P element and C element is (x+3y)～1.1 (x+3y): x:2y:0.1 (x+y)～0.5 (x+y): (x+3y): 0.5 (x+3y)～2 (x+3y) ratio takes by weighing the lithium source, source of iron, vanadic salts, magnesium salts, mix after source of phosphoric acid and the carbon source and obtain mixture, then mixture is placed ball mill, carry out wet-milling 2～12h after adding dispersant, namely obtain compound, wherein the volume ratio of dispersant and mixture is 1～10:1, dispersant is absolute ethyl alcohol, acetone or water, 0.05≤x/ (x+y)≤0.95; Two, under the protection of 250～450 ℃ and protection gas, compound presintering 2～6h that step 1 is obtained; Three, the compound after presintering is handled is then calcined 6～30h under the protection of 570～870 ℃ and protection gas, be cooled to room temperature, makes xLiFePO
4YLi
3V
2(PO
4)
3
The used abrading-ball of present embodiment wet-milling can adopt steel ball, agate ball or zirconium ball, and ball material mass ratio is 1:1.
Embodiment two: what present embodiment and embodiment one were different is: the described lithium of step 1 source is LiOHH
2O, LiF, Li
2CO
3, LiCH
3COOH
2O and LiNO
3In a kind of or wherein several combination.Other step is identical with embodiment one with parameter.
When the lithium source is mixture in the present embodiment, press between various lithiums source arbitrarily than mixing.The magnesium doping xLiFePO of present embodiment preparation
4YLi
3V
2(PO
4)
3Higher first discharge specific capacity and capability retention are arranged, the magnesium doping xLiFePO of preparation
4YLi
3V
2(PO
4)
3The first discharge specific capacity of electrode is 130mAh g
-1After 400 circulations, the former is not less than 95% by capability retention.And find this good multiplying power discharging property that just having, during the 10C discharge, specific discharge capacity is 90mAhg
-1, 20 times circulation back capacity is decayed hardly.
Embodiment three: what present embodiment was different with embodiment one or two is: the described source of iron of step 1 is ferrous oxalate, ferric phosphate, hypophosphite monohydrate iron, ferric nitrate or iron oxide.Other step is identical with embodiment one or two with parameter.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the described vanadium of step 1 source is V
2O
5, VO
2, V
2O
3, carbonic acid vanadium or NH
4VO
3Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the described phosphate of step 1 is NH
4H
2PO
4, (NH
4)
2HPO
4, (NH
4)
3PO
4Or P
2O
5Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: the used protection gas of step 2 presintering is decomposed ammonia, argon gas, nitrogen or hydrogen-argon-mixed.Other step is different with one of embodiment one to five with parameter.
When hydrogen-argon-mixed, hydrogen and argon gas are pressed arbitrarily than mixing.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: the described pre-burning of step 2 is become 300～400 ℃.Other step is different with one of embodiment one to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: the carbon source described in the step 3 is a kind of in sucrose, citric acid, carbon nano-tube, acetylene black, graphite and the super conductive black (Super-P) or wherein several combination; When carbon source was carbon nano-tube and sucrose mixing, carbon nano-tube accounted for 20%～99% of carbon source gross mass.Other step is identical with one of embodiment one to seven with parameter.
Except carbon nano-tube and sucrose mix by the said ratio combination situations, when carbon source is mixture in the present embodiment, between various carbon sources by arbitrarily than mixing.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: the calcining heat in the step 3 is 650～750 ℃.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what present embodiment was different with one of embodiment one to nine is: the used protection gas of step 3 presintering is decomposed ammonia, argon gas, nitrogen or hydrogen-argon-mixed.Other step is identical with one of embodiment one to nine with parameter.
When hydrogen-argon-mixed, hydrogen and argon gas are pressed arbitrarily than mixing.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is: the described magnesium salts of step 1 is magnesium acetate, basic magnesium carbonate or magnesium nitrate.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 12: anode material for lithium-ion batteries magnesium doping 7LiFePO in the present embodiment
4Li
3V
2(PO
4)
3The preparation method carry out in following step: one, mix obtaining mixture after lithium hydroxide, ferric phosphate, vanadic oxide, magnesium nitrate, ammonium dihydrogen phosphate and the sucrose for the 10:7:2:0.5:10:11 ratio takes by weighing in the mol ratio of Li element, Fe element, V element, Mg element, P element and C element, then mixture is placed ball mill, carry out wet-milling 2～12h after adding dispersant, namely obtain compound, wherein the volume ratio of dispersant and mixture is 1～10:1, and dispersant is absolute ethyl alcohol; Two, under the protection of 350 ℃ and protection gas, the compound presintering 4h that step 1 is obtained; Three, then 770 ℃ and the protection gas protection under calcine 12h, be cooled to room temperature, make magnesium doping 7LiFePO
4Li
3V
2(PO
4)
3
Product to present embodiment detects, and the results are shown in Figure 1-3:
As seen from Figure 1, the method sintetics of present embodiment is the mixture of olivine structural and monocline.
As shown in Figure 2, under 1C (1C is equivalent to 150mA/g) multiplying power, the magnesium doping 7LiFePO of preparation
4Li
3V
2(PO
4)
3The first discharge specific capacity of electrode is 130mAh/g.
As seen from Figure 3, in the charge-discharge test of different multiplying (1C, 3C, 5C and 10C), magnesium doping 7LiFePO
4Li
3V
2(PO
4)
3Material list reveals high discharge capacity and good high rate performance.
As seen from the figure, this synthetic method not only is fit to large batch of industrial production, and is simple to operate, environment-friendly, and synthetic product has excellent high rate during charging-discharging.
Claims (1)
1. magnesium doping xLiFePO
4YLi
3V
2(PO
4)
3The preparation method of anode material for lithium-ion batteries is characterized in that magnesium doping xLiFePO
4YLi
3V
2(PO
4)
3The preparation method of anode material for lithium-ion batteries carries out in following step: one, mix obtaining mixture after lithium hydroxide, ferric phosphate, vanadic oxide, magnesium nitrate, ammonium dihydrogen phosphate and the sucrose for the 10:7:2:0.5:10:11 ratio takes by weighing in the mol ratio of Li element, Fe element, V element, Mg element, P element and C element, then mixture is placed ball mill, carry out wet-milling 2～12h after adding dispersant, namely obtain compound, wherein the volume ratio of dispersant and mixture is 1～10:1, and dispersant is absolute ethyl alcohol; Two, under the protection of 350 degrees centigrade and protection gas, the compound presintering 4h that step 1 is obtained; Three, then 770 degrees centigrade and the protection gas protection under calcine 12h, be cooled to room temperature, make magnesium doping 7LiFePO
4Li
3V
2(PO
4)
3
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Non-Patent Citations (9)
| Title |
|---|
| changsong dai,etal.Synthesis and performance of Li3(V1− |
| Synthesis and performance of Li3(V1−xMgx)2(PO4)3 cathode materials;changsong dai,etal;《Journal of Power Sources》;20100306;第5775-5779页 * |
| xMgx)2(PO4)3 cathode materials.《Journal of Power Sources》.2010,第5775-5779页. |
| 以碱式碳酸镁为镁源的镁掺杂磷酸钒锂的研究;戴长松等;《2009年第十五次全国电化学学术会议论文集》;20091201;1页 * |
| 刘恒等.改进的固相法制备磷酸铁锂电池材料.《四川大学学报(工程科学版)》.2004,第36卷(第4期),第74-77页. |
| 戴长松等.以碱式碳酸镁为镁源的镁掺杂磷酸钒锂的研究.《2009年第十五次全国电化学学术会议论文集》.2009,1页. |
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| 镁离子掺杂磷酸钒锂的中试合成及性能研究;戴长松等;《第28届全国化学与物理电源学术年会论文集》;20091101;第201-202页 * |
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