CN107834030A - 一种添加纳米二氧化钛制备复合电极材料及工艺 - Google Patents
一种添加纳米二氧化钛制备复合电极材料及工艺 Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- -1 Rare earth ion Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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Abstract
本发明公开了一种添加纳米二氧化钛制备复合电极材料及工艺。该材料是以LiOH为锂源,Fe(PO4)3作为铁源,(NH4)2HPO4为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,按照Li1‑xNd xFe1‑yTiyPO4的原子配比制备的一种复合电极材料。先按照原子配比配料,然后通过球磨工艺球磨制备浆料,将浆料干燥后在惰性气氛保护下进行热处理、冷却即可制备目标产物。此方法工艺简单,复合电极材料粉末性能良好。
Description
技术领域
本发明涉及一种锂离子复合电极材料及其制备工艺,特别涉及一种掺杂钛元素的锂离子复合电极材料及制备方法,属于电极材料加工领域。
背景技术
锂离子电池是是一种二次电池(充电电池),它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中,Li+ 在两个电极之间往返嵌入和脱嵌:充电时,Li+从正极脱嵌,经过电解质嵌入负极,负极处于富锂状态,放电时则相反。以 LiFePO4为代表的聚阴离子结构磷酸盐材料,其突出的安全性、超长循环寿命、低成本等特点在锂离子电子领域受到了广泛关注。
LiFePO4具有稍微扭曲的六方密堆积排列结构,属于正交晶系,在锂原子所在的a-c 平面中,包含有 PO4四面体,这就限制了锂离子的移动空间,导致锂离子迁移速率和电子电导率均偏低,制约了LiFePO4锂电池的应用范围。
有文献(稀土金属离子掺杂对LiFePO4结构和性能的影响,《稀有金属材料与工程》,2011,40 (11):1936-1940)指出:将稀土金属离子对LiFePO4的Li原子位进行掺杂,通过X射线衍射(XRD)、恒电流充放电及电化学阻抗(EIS)法系统分析表明:掺杂后的试样的性能得到了很大的提高。因此在实际制备过程中往往添加稀土元素,改善LiFePO4电极材料的性能。但是单添加稀土元素,对LiFePO4的导电率性能改善单一, LiFePO4电极材料的应用得不到进一步提升。
发明内容
本发明通过球磨工艺及高温固相法制备一种Li1-xNdxFe1-yTiyPO4复合电极材料,并在制备过程中添加稀土Nd粉和纳米二氧化钛粉末,从而掺杂Nd和Ti原子,制备Li1-xNdxFe1- yTiyPO4复合电极材料,提高LiFePO4的导电及充放电性能。此方法工艺简单,前驱体混合程度良好,生产成本低,制备的电极材料循环及容量性能良好。该电极材料粉体的制备工艺包括如下步骤:
⑴以LiOH作为锂源,以Fe(PO4)3作为铁源,(NH4)2HPO4作为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,各成分按照Li1-xNd xFe1-yTiyPO4(0.02≤x≤0.1, 0.2≤y≤0.4)的原子比配料,然后取一定量的配好的原料用球磨罐进行球磨;
⑵将球磨后制得的浆料混合物进行干燥,干燥后得到前驱体粉末;
⑶ 将制备的前驱体粉末在惰性气氛保护下于进行热处理;
⑷经过热处理工艺后,将所得产物在惰性气氛保护下自然冷却至室温,收集粉末即得到一种Li1-xNd xFe1-yTiyPO4复合电极材料粉末。
在上述电极材料粉体的制备工艺步骤⑴中,所述球磨过程需要加入球磨介质无水酒精或者丙酮,机械球磨时间为10-15小时。在上述电极材料粉体的制备工艺步骤⑵中,所述对混合浆料干燥是采用喷雾干燥。在上述电极材料粉体的制备工艺步骤⑶中,所述对前驱体粉末进行热处理工艺是在氮气、氩气或者两者的混合气体条件下,先在500-600℃的条件下进行热处理5-8h,然后将温度升高至700-800℃,热处理10-15h。在上述电极材料粉体的制备工艺步骤⑷中,所述惰性气氛保护下是在氮气、氩气或者两者的混合气体条件下。
实施例一:
以LiOH作为锂源,以Fe(PO4)3作为铁源,(NH4)2HPO4作为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,按照Li0.98Nd0.02Fe0.8Ti0.2PO4的原子配比配料5g的混合物,将配好的混合物原料进行初步混合后一起倒入球磨罐中,再往球磨罐中添加适量钢球和无水酒精作为球磨介质,然后盖上球磨罐盖子并拧紧螺丝,拧紧后再将其放入行星式球磨机中进行球磨10小时,球磨结束后取下球磨罐静置一段时间后,打开球磨罐,将球磨罐中合金微粉浆料取出进行喷雾干燥得前驱体粉末,再将粉末在氮气的保护条件下进行高温加热至500℃,恒温5小时,然后升高温度至700℃,恒温10小时,所得产物在氮气气氛保护下自然冷却至室温,收集粉末即得产品。
实施例二:
以LiOH作为锂源,以Fe(PO4)3作为铁源,(NH4)2HPO4作为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,按照Li0.95Nd0.05Fe0.7Ti0.3PO4的原子配比配料20g的混合物,将配好的混合物原料进行初步混合后一起倒入球磨罐中,再往球磨罐中添加适量钢球和无水酒精球磨介质,然后盖上球磨罐盖子并拧紧螺丝,拧紧后再将其放入行星式球磨机中进行球磨12小时,球磨结束后取下球磨罐静置一段时间后,打开球磨罐,将球磨罐中合金微粉浆料取出进行喷雾干燥得前驱体粉末,再将粉末在氮气的保护条件下进行高温加热至550℃,恒温6小时,然后升高温度至750℃,恒温12小时,所得产物在氮气气氛保护下自然冷却至室温,收集粉末即得产品。
实施例三:
以LiOH作为锂源,以Fe(PO4)3作为铁源,(NH4)2HPO4作为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,按照Li0.9Nd0.1Fe0.6Ti0.4PO4的原子配比配料50g的混合物,将配好的混合物原料进行初步混合后一起倒入球磨罐中,再往球磨罐中添加适量钢球和丙酮球磨介质,然后盖上球磨罐盖子并拧紧螺丝,拧紧后再将其放入行星式球磨机中进行球磨15小时,球磨结束后取下球磨罐静置一段时间后,打开球磨罐,将球磨罐中合金微粉浆料取出进行喷雾干燥得前驱体粉末,再将前驱体粉末装入一端封口的石英玻璃管中,往内充满适量氮气,再用高温火焰熔融石英管开口另一端使其密封,将密封的石英玻璃管投入水中验证气密性,若无气泡,则可认定其密封性良好,在将粉末在氮气的保护条件下进行高温加热至600℃,恒温8小时,然后升高温度至800℃,恒温15小时,所得产物在氮气气氛保护下自然冷却至室温,收集粉末即得产品。
Claims (5)
1.一种Li1-xNdxFe1-yTiyPO4复合电极材料,其特征在于该复合电极材料的制备方法按如下步骤进行:
⑴以LiOH作为锂源,以Fe(PO4)3作为铁源,(NH4)2HPO4作为磷酸源,Nd粉作为掺杂Nd的掺杂原料,纳米二氧化钛粉末作为掺杂Ti的掺杂原料,各成分按照Li1-xNd xFe1-yTiyPO4(0.02≤x≤0.1, 0.2≤y≤0.4)的原子比配料,然后取一定量的配好的原料用球磨罐进行球磨;
⑵将球磨后制得的浆料混合物进行干燥,干燥后得到前驱体粉末;
⑶ 将制备的前驱体粉末在惰性气氛保护下于进行热处理;
⑷经过热处理工艺后,将所得产物在惰性气氛保护下自然冷却至室温,收集粉末即得到一种Li1-xNd xFe1-yTiyPO4复合电极材料粉末。
2.如权利要求1所述的一种Li1-xNdxFe1-yTiyPO4复合电极材料,其特征在于,在制备工艺步骤⑴中,所述球磨过程需要加入球磨介质无水酒精或者丙酮,机械球磨时间为10-15小时。
3.如权利要求1或者2所述的一种Li1-xNdxFe1-yTiyPO4复合电极材料,其特征在于,在材料制备的步骤⑵中,所述对混合浆料干燥是采用喷雾干燥。
4.如权利要求1或者2所述的一种Li1-xNdxFe1-yTiyPO4复合电极材料,其特征在于,在制备工艺步骤⑶中,所述对前驱体粉末进行热处理工艺是在氮气、氩气或者两者的混合气体条件下,先在500-600℃的条件下进行热处理5-8h,然后将温度升高至700-800℃,热处理10-15h。
5.如权利要求1或者2所述的一种Li1-xNdxFe1-yTiyPO4复合电极材料,其特征在于,在制备工艺步骤⑷中,所述惰性气氛保护下是在氮气、氩气或者两者的混合气体条件下。
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CN1837033A (zh) * | 2006-03-24 | 2006-09-27 | 山东科技大学 | 锂离子电池正极材料磷酸亚铁锂的合成方法 |
CN101339994A (zh) * | 2008-09-01 | 2009-01-07 | 罗绍华 | 多位掺杂型磷酸铁锂正极材料制备方法及其应用 |
CN101800315A (zh) * | 2010-04-09 | 2010-08-11 | 曲阜毅威能源股份有限公司 | 一种多元素掺杂磷酸铁锂正极材料及其制备方法 |
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CN1837033A (zh) * | 2006-03-24 | 2006-09-27 | 山东科技大学 | 锂离子电池正极材料磷酸亚铁锂的合成方法 |
CN101339994A (zh) * | 2008-09-01 | 2009-01-07 | 罗绍华 | 多位掺杂型磷酸铁锂正极材料制备方法及其应用 |
CN101800315A (zh) * | 2010-04-09 | 2010-08-11 | 曲阜毅威能源股份有限公司 | 一种多元素掺杂磷酸铁锂正极材料及其制备方法 |
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