CN108217618A - 一种掺杂稀土元素的磷酸铁锂复合电极材料 - Google Patents
一种掺杂稀土元素的磷酸铁锂复合电极材料 Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 19
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- -1 compound ion Chemical class 0.000 claims description 3
- 229910000904 FeC2O4 Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 230000037351 starvation Effects 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910017677 NH4H2 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003595 mist Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Crystallography & Structural Chemistry (AREA)
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Abstract
本发明提供杂一种掺杂稀土元素的磷酸铁锂复合电极材料。磷酸铁锂材料电导率低，放电电压低，本方法通过掺杂稀土La和Ce，制备一种磷酸铁锂复合电极材料，该工艺简单，制备的电极材料电导率高、成分均匀，且制备工艺简单，具有良好的应用前景。
Description
技术领域
本发明涉及一种锂离子电极材料及其制备方法，特别涉及一种掺杂稀土元素的锂离子复合电极材料及其制备方法，属于电池领域。
背景技术
1912年锂金属电池最早由Gilbert N. Lewis提出并研究，由于锂金属的化学特性非常活泼，使得对环境要求非常高，所以，锂电池长期没有得到应用。后来，日本索尼公司发明了以炭材料为负极，以含锂的化合物作正极的锂电池，在充放电过程中，没有金属锂存在，只有锂离子，这就是锂离子电池。当对电池进行充电时，电池的正极上有锂离子生成，生成的锂离子经过电解液运动到负极。而作为负极的碳呈层状结构，它有很多微孔，达到负极的锂离子就嵌入到碳层的微孔中，嵌入的锂离子越多，充电容量越高。
磷酸铁锂材料由于安全性高、成本较低被广泛应用，但存在室温电导率低，放电电压低（3.4V）等缺点，都制约了自身的进一步应用。材料的选择是影响锂离子电池性能的第一要素，从材料角度来看，LiFePO4具有稍微扭曲的六方密堆积排列结构，属于正交晶系，空间群为 Pnma。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，因此它的电导率比其它的层状化合物低。
有文献指出，稀土元素能够代替了Li的位置，很好的融入到橄榄石结构中，且能够改提高LiFePO4的导电率。本发明通过球磨工艺、高温固相法掺杂稀土La和Ce原子，制备一种磷酸铁锂复合电极材料。
发明内容
本发明的目的是提供一种掺杂稀土元素的磷酸铁锂复合电极材料及其制备方法。该制备方法包括如下步骤：
⑴以Li2CO3、FeC2O4・2H2O 、Li2CO3、NH4H2PO4、稀土La和稀土Ce粉末作为原料，依照Li1-（x+y）FeLaxCeyPO4（0.01≤x+y≤0.1）的原子配例称取样品；
⑵将原料混合物和适量蔗糖倒入一球磨罐中，再投入一定质量比例的钢球，在汽油的保护下进行球磨；
⑶球磨一段时间后，把球磨后的合金微粉晾干；
⑷将晾干的粉末在隔绝氧气的条件下高温煅烧，煅烧后即得一种复合离子电极材料。
优先地，在步骤⑵中，蔗糖与原料的添加比例为0.2-0.3，球料比为15-20。
优先地，在步骤⑵中，行星式球磨机速度控制250-350 r/min运行。
优先地，在步骤⑵中，用行星式球磨机进行球磨的时间为20-40h。
优先地，在步骤⑷中，高温煅烧温度为600-900℃，煅烧时间为30-50h。
本发明具有下列优点和特性：
⑴制备的电极材料粉末电率高，容量大；
⑵重现性好，条件容易控制；
⑶制备工艺简单，易操作；
⑷流程短，易于实现工业化。
实施例一：
取适量化学纯的FeC2O4・2H2O 、Li2CO3、NH4H2PO4和稀土金属La、Ce粉末作为原料，按照Li0.9FeLa0.01Ce0.09PO4的原子比例配料5g的原料，取一球磨罐，将配好5g原料的混合物和1.5g的蔗糖倒入罐中，再投入100g的钢球，然后用汽油装满罐，将盖盖紧后，放置球磨机上球磨，球磨速度设置250 r/min，球磨40h后，取出球磨罐，打开罐盖，倒出上层液体，让底层合金微粉自然晾干，待充分晾干后，将合金粉末装入充满氩气的石英玻璃管中并密封，然后把石英玻璃管放入600℃高温炉中进行烧结50h，烧结后待冷却，取出管内粉末即得一种磷酸铁锂复合电极材料。
实施例二：
取适量化学纯的FeC2O4・2H2O 、Li2CO3、NH4H2PO4和稀土金属La、Ce粉末作为原料，按照Li0.9FeLa0.01Ce0.09PO4的原子比例配料10g的原料，取一球磨罐，将配好10g原料的混合物和3g的蔗糖倒入罐中，再投入150g的钢球，然后用汽油装满罐，将盖盖紧后，放置球磨机上球磨，球磨速度设置300 r/min，球磨30h后，取出球磨罐，打开罐盖，倒出上层液体，让底层合金微粉自然晾干，待充分晾干后，将合金粉末装入充满氩气的石英玻璃管中并密封，然后把石英玻璃管放入800℃高温炉中进行烧结40h，烧结后待冷却，取出管内粉末即得一种磷酸铁锂复合电极材料。
实施例三：
取适量化学纯的FeC2O4・2H2O 、Li2CO3、NH4H2PO4和稀土金属La、Ce粉末作为原料，按照Li0.9FeLa0.01Ce0.09PO4的原子比例配料20g的原料，取一球磨罐，将配好20g原料的混合物和20g的蔗糖倒入罐中，再投入300g的钢球，然后用汽油装满罐，将盖盖紧后，放置球磨机上球磨，球磨速度设置350 r/min，球磨20h后，取出球磨罐，打开罐盖，倒出上层液体，让底层合金微粉自然晾干，待充分晾干后，将合金粉末装入充满氩气的石英玻璃管中并密封，然后把石英玻璃管放入900℃高温炉中进行烧结30h，烧结后待冷却，取出管内粉末即得一种磷酸铁锂复合电极材料。
Claims (5)
1.一种掺杂稀土元素的磷酸铁锂复合电极材料，其特征在于该电极材料的制备工艺按如下步骤进行：
⑴以Li2CO3、FeC2O4・2H2O 、Li2CO3、NH4H2PO4、稀土La和稀土Ce粉末作为原料，依照Li1-（x+y）FeLaxCeyPO4（0.01≤x+y≤0.1）的原子配例称取样品；
⑵将原料混合物和适量蔗糖倒入一球磨罐中，再投入一定质量比例的钢球，在汽油的保护下进行球磨；
⑶球磨一段时间后，把球磨后的合金微粉晾干；
⑷将晾干的粉末在隔绝氧气的条件下高温煅烧，煅烧后即得一种复合离子电极材料。
2.如权利要求1所示的一种掺杂稀土元素的磷酸铁锂复合电极材料，其特征在于，制备方法的步骤⑵中，蔗糖与原料的添加比例为0.2-0.3，球料比为15-20。
3.如权利要求1所示的一种掺杂稀土元素的磷酸铁锂复合电极材料，其特征在于，制备方法的步骤⑵中，行星式球磨机速度控制250-350 r/min运行。
4.如权利要求1所示的一种掺杂稀土元素的磷酸铁锂复合电极材料，其特征在于，制备方法的步骤⑵中，用行星式球磨机进行球磨的时间为20-40h。
5.如权利要求1所示的一种掺杂稀土元素的磷酸铁锂复合电极材料，其特征在于，制备方法的步骤⑷中，高温煅烧温度为600-900℃，煅烧时间为30-50h。
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