CN111689773A - 一种微波快速烧结制备llzo固体电解质的方法 - Google Patents
一种微波快速烧结制备llzo固体电解质的方法 Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 24
- 238000005245 sintering Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009768 microwave sintering Methods 0.000 claims abstract description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 3
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000002001 electrolyte material Substances 0.000 claims abstract 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 8
- 239000013589 supplement Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000002223 garnet Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 25
- 238000000498 ball milling Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
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- 238000000840 electrochemical analysis Methods 0.000 description 5
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- 239000002184 metal Substances 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 3
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- 229910010685 Li5La3M2O12 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- -1 Sm-Lu) (Li 3 system) Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
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- 238000000265 homogenisation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种通过微波快速烧结制备LLZO（Li7La3Zr2O12）固体电解质的方法，该方法利用传统固相法，通过压制成型和新型微波烧结法，制备出一种LLZO固体电解质陶瓷材料。该材料具有典型的立方相石榴石结构，具有较高的离子电导率，此外该电解质材料还展现出了机械强度高，工作温度范围广的优点，是一种优秀的锂离子电池固体电解质材料。
Description
技术领域
本发明具体涉及一种锂离子固体电解质材料Li7La3Zr2O12的制备方法，属于锂离子电池技术领域。
背景技术
随着便携式电子设备，如笔记本电脑、智能手机的发展，锂离子电池在多个领域得到越来越多的应用。未来的锂离子电池将逐步向以下两个方向发展：用于微型电子设备的小/微型电池和作为储能与动力电池用的大型储能/动力系统。传统的电池使用的电解液一般是溶有锂盐的有机物，稳定性较差，此外目前使用较多的有机电解液还具有较强的腐蚀性与易燃性，虽然采用特殊保护措施等方法，仍然面临一定风险。
相对而言，使用固体电解质安全性能好、无泄漏风险，这提高了电池的安全性能和使用年限。但是固体电解质体系仍然面临较低的锂离子电导率以及电极/固体电解质（固-固）界面等突出问题。其中以LLZO为代表的石榴石结构材料具有良好的锂离子迁移率，是固体电解质的优异材料。
石榴石(garnet)的化学通式为A3B2(XO4)3（A=Ca、Mg、Y、La或其它稀土元素；B=Fe、Ge、Mn、Ga、Al、Ni或者V），其中，A、B、X均为阳离子占据位置，分别有8、6、4个氧配位，当X为Li+时，石榴石具有Li+导通能力，石榴石每结构单元可以含有5~7个Li+，超过了传统石榴石结构所能容纳的3个Li+。根据Li+在石榴石结构中的浓度，大致可分为以下几类：Li3Ln3Te2O12（Ln=Y、Pr、Nd、Sm-Lu）（Li3体系）、Li5La3M2O12（M=Nb、Ta、Sb、Bi）（Li5体系）、Li6ALa2M2O12（A=Ca、Sr、Ba；M=Nb、Ta）（Li6体系）和Li7La3C2O12（C=Zr、Sn、Hf）（Li7体系）。但是制备石榴石结构的LLZO材料仍然面临着传统烧结方法制备周期长、效果差等缺点。因此，在上述基础上，为了提升锂离子固体电解质材料的电化学性能，我们提出了一种微波快速烧结制备LLZO固体电解质的方法。
发明内容
本发明针对锂离子液体电解质电池的局限性和传统制备方法制备的锂离子固体电解质电池电导率低的问题，提供了一种利用压制成型结合微波烧结的方法，制备出具有高离子迁移率的锂离子固体电解质Li7La3Zr2O12。
具体实施技术方案：
（1）按照化学计量比为7:3:2分别称取碳酸锂、六水硝酸镧、二氧化锆，由于碳酸锂在高温过程中容易挥发，因此在配置原料需要适当进行补锂，碳酸锂补锂量为10 ％（可以取15％，20 ％）。
（2）将称量的三种原料依次放进玛瑙球磨罐里，加入玛瑙球磨石和作为分散剂的乙醇进行球磨（料球醇比为1:2:1），球磨时间为100 min，转速为400 rpm，球磨后的浆料过筛后在80 ℃下干燥12 h。
（3）在得到的粉体中加入3 %的质量浓度为5 %的PVP水溶液，充分研磨后在直径为15 mm的模具中压片，压力设置为8 MPa，保压时间为1 min。
（4）将得到的陶瓷片置于马弗炉中进行排胶，排胶温度为600 ℃，保温1 h，升温速率为1 ℃·min-1。
（5）在氧化铝坩埚中放入提前制备好的LLZO粉体作为母粉，将排胶后的陶瓷片埋入母粉中，放入微波快速烧结炉中进行快速烧结，升温速率为30 ℃·min-1，烧结温度为1150 ℃（可以选择为1125 ℃、1175 ℃、1120 ℃），保温1 h（2 h、3 h、4 h）。
（6）经自然冷却后的LLZO陶瓷经抛光后在充满氩气的手套箱中与金属锂片组装成对称扣式电池，并进行电化学测试。
本发明的显著优点：
（1）采用碳酸锂、六水硝酸镧、二氧化锆作为原料，价格低廉，降低了成本；
（2）采用简单易操作的压制成型法，生产工艺简单，制备过程易于操作，适合大规模工业化生产；
（3）采用微波烧结的烧结工艺，具有降低烧结温度，减少能耗，缩短烧结时间50 %以上，且微波烧结可以显著提高材料致密度、细化晶粒、工艺精确可控的优点，并能够改善材料电化学性能。
（4）制备的Li7La3Zr2O12锂离子固体电解质具有立方相的晶体结构和高的Li离子含量的优点，且机械强度高，工作温度区间宽，是一种优秀的锂离子固体电解质。
具体实施方案：
实施例1：
（1）按照化学计量比为7:3:2分别称取碳酸锂、六水硝酸镧、二氧化锆5.17g、12.9g、2.46g，碳酸锂补锂量为10 %，即再加入碳酸锂0.517g。
（2）将称量的三种原料依次放进玛瑙球磨罐里，加入玛瑙球磨石和作为分散剂的乙醇进行球磨（料球醇比为1:2:1），球磨时间为100 min，转速为400 rpm，球磨后的浆料过筛后在80 ℃下干燥12 h。
（3）在得到的粉体中加入3 %的质量浓度为5 %的PVP水溶液，充分研磨后在直径为15 mm的模具中压片，压力设置为8 MPa，保压时间为1 min。
（4）将得到的陶瓷片置于马弗炉中进行排胶，排胶温度为600 ℃，保温1 h，升温速率为1 ℃·min-1。
（5）在氧化铝坩埚中放入提前制备好的LLZO粉体作为母粉，将排胶后的陶瓷片埋入母粉中，放入微波快速烧结炉中进行快速烧结，升温速率为30 ℃·min-1，烧结温度为1150 ℃，保温1 h。
（6）经自然冷却后的LLZO陶瓷经抛光后在充满氩气的手套箱中与金属锂片组装成对称扣式电池，并进行电化学测试。
实施例2：
（1）按照化学计量比为7:3:2分别称取碳酸锂、六水硝酸镧、二氧化锆5.17 g、12.9 g、2.46 g，碳酸锂补锂量为10 %，即再加入碳酸锂0.517 g。
（2）将称量的三种原料依次放进玛瑙球磨罐里，加入玛瑙球磨石和作为分散剂的乙醇进行球磨（料球醇比为1:2:1），球磨时间为100 min，转速为400 rpm，球磨后的浆料过筛后在80 ℃下干燥12 h。
（3）在得到的粉体中加入3 %的质量浓度为5 %的PVP水溶液，充分研磨后在直径为15 mm的模具中压片，压力设置为8 MPa，保压时间为1 min。
（4）将得到的陶瓷片置于马弗炉中进行排胶，排胶温度为600 ℃，保温1 h，升温速率为1 ℃·min-1。
（5）在氧化铝坩埚中放入提前制备好的LLZO粉体作为母粉，将排胶后的陶瓷片埋入母粉中，放入微波快速烧结炉中进行快速烧结，升温速率为30 ℃·min-1，烧结温度为1175 ℃，保温1 h。
（6）经自然冷却后的LLZO陶瓷经抛光后在充满氩气的手套箱中与金属锂片组装成对称扣式电池，并进行电化学测试。
实施例3：
（1）按照化学计量比为7:3:2分别称取碳酸锂、六水硝酸镧、二氧化锆5.17 g、12.9 g、2.46 g，碳酸锂补锂量为15 %，即再加入碳酸锂0.776 g。
（2）将称量的三种原料依次放进玛瑙球磨罐里，加入玛瑙球磨石和作为分散剂的乙醇进行球磨（料球醇比为1:2:1），球磨时间为100 min，转速为400 rpm，球磨后的浆料过筛后在80 ℃下干燥12 h。
（3）在得到的粉体中加入3 %的质量浓度为5 %的PVP水溶液，充分研磨后在直径为15 mm的模具中压片，压力设置为8 MPa，保压时间为1 min。
（4）将得到的陶瓷片置于马弗炉中进行排胶，排胶温度为600 ℃，保温1 h，升温速率为1 ℃·min-1。
（5）在氧化铝坩埚中放入提前制备好的LLZO粉体作为母粉，将排胶后的陶瓷片埋入母粉中，放入微波快速烧结炉中进行快速烧结，升温速率为30 ℃·min-1，烧结温度为1175 ℃，保温1 h。
（6）经自然冷却后的LLZO陶瓷经抛光后在充满氩气的手套箱中与金属锂片组装成对称扣式电池，并进行电化学测试。
实施例4：
（1）按照化学计量比为7:3:2分别称取碳酸锂、六水硝酸镧、二氧化锆5.17 g、12.9 g、2.46 g，碳酸锂补锂量为20 %，即再加入碳酸锂1.034 g。
（2）将称量的三种原料依次放进玛瑙球磨罐里，加入玛瑙球磨石和作为分散剂的乙醇进行球磨（料球醇比为1:2:1），球磨时间为100 min，转速为400 rpm，球磨后的浆料过筛后在80 ℃下干燥12 h。
（3）在得到的粉体中加入3 %的质量浓度为5 %的PVP水溶液，充分研磨后在直径为15 mm的模具中压片，压力设置为8 MPa，保压时间为1 min。
（4）将得到的陶瓷片置于马弗炉中进行排胶，排胶温度为600 ℃，保温1 h，升温速率为1 ℃·min-1。
（5）在氧化铝坩埚中放入提前制备好的LLZO粉体作为母粉，将排胶后的陶瓷片埋入母粉中，放入微波快速烧结炉中进行快速烧结，升温速率为30 ℃·min-1，烧结温度为1175 ℃，保温2 h。
（6）经自然冷却后的LLZO陶瓷经抛光后在充满氩气的手套箱中与金属锂片组装成对称扣式电池，并进行电化学测试。
附图说明：
图1是本发明合成的LLZO固体电解质材料的SEM图。从电镜图中可以看出，材料颗粒大小均匀，致密度较高，说明通过微波烧结法可以实现材料晶粒的均匀化，并提高陶瓷材料的致密度，这为提高材料的锂离子迁移率提供了基础。
图2是本发明合成的LLZO固体电解质材料的XRD图，图中产物的谱图与标准谱图一致。所制备的材料展现出所有立方相LLZO的特征峰，说明通过微波烧结过程能够在较短时间内制备出立方相的LLZO材料。
图3是本发明合成的LLZO固体电解质材料用于作锂离子电池时的尼奎斯特图。从尼奎斯特图中看出以制备的LLZO作为隔膜制备的对称扣式电池具有理想的曲线形状，且在电池内阻和离子迁移率方面展现了优异的性能，材料的内阻约为1.15×105 Ω，经过拟合后计算的得到材料的离子迁移率约为3.67×10-7 S/cm。
Claims (7)
1.一种用作锂离子电池电解质材料，其特征在于，所述的电解质材料是Li7La3Zr2O12陶瓷材料。
2.根据权利要求1所述的一种用作锂离子电池电解质材料，其特征在于，将Li7La3Zr2O12固体电解质应用在锂离子电池中。
3.根据权利要求1所述的一种用作锂离子电池电解质材料，其特征在于，所述Li7La3Zr2O12固体电解质为立方相。
4.根据权利要求1所述的一种用作锂离子电池电解质材料，其特征在于，所述Li7La3Zr2O12固体电解质为压制成型后，经过微波烧结过程得到的。
5.根据权利要求1所述的一种用作锂离子电池电解质材料，其特征在于，所述Li7La3Zr2O12固体电解质原理配比中碳酸锂补锂量为10 %-20%。
6.根据权利要求3所述的一种用作锂离子电池电解质材料，其特征在于，所述Li7La3Zr2O12固体电解质立方相的烧结温度为烧结温度为1150-1120 ℃，保温1-4 h。
7.根据权利要求4所述的一种用作锂离子电池电解质材料，其特征在于，所述Li7La3Zr2O12固体电解质压制成型的压力为8 MPa，保压时间为1 min。
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