CN101567449B - 一种纳米级锂电池正极材料及其制备方法 - Google Patents
一种纳米级锂电池正极材料及其制备方法 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 34
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 239000002019 doping agent Substances 0.000 claims description 38
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
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- 239000008103 glucose Substances 0.000 claims description 10
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- -1 iron ion Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000002253 acid Substances 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 description 3
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- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
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- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229940029985 mineral supplement Drugs 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种纳米级锂电池正极材料及其制备方法，该材料以锂铁磷酸盐为基材，还掺有导电掺杂离子和增压掺杂离子，化学通式为：(Lix[M1-x])(Fey[N1-y])PO4，式中：x＝0.9～0.96；y＝0.93～0.97；M为导电掺杂离子；N为增压掺杂离子。该材料通过固相反应制得：所有原料混合均匀-碎成粉体-压粒-惰性氛围200～400℃恒温烧结2～3小时-冷却-碎成粉体-压粒-惰性氛围500～780℃恒温烧结15～20小时-冷却-碎成粉体-气流粉碎、分级。本方法生产成本低、操作简单、环保、成品率高。通过本固相反应制成的纳米级锂电池正极材料，其导电率优于10-2S/cm，实际放电容量＞250mAh/g，可快速大功率充放电，具有低价、高能、安全、环保等特征，适用于小型聚合物、胶体和液体锂离子电池，尤其适用于大功率动力电池。
Description
技术领域
本发明涉及一种纳米级锂电池正极材料及其制备方法，该材料用于聚合物、胶体和液体锂离子电池中，特别适用于制作大功率的动力电池。
背景技术
目前，锂电池中常用的正极材料有三种：钴酸锂、镍钴酸锂和锰酸锂。钴酸锂和镍钴酸锂是六方晶系层状岩盐结构的氧化物，锂离子中的电子在O-Co-O构成的八面体层间隙中移动，具有较高的导电性能和锂离子脱嵌/嵌入的可逆性。锰酸锂是尖晶石三维结构的氧化物，锂离子中的电子在O-Mn-O构成的八面体立方通道中移动，也具有较高的导电性能和锂离子脱嵌/嵌入可逆性。它们都是当前锂电池工业中大量应用的正极材料。但金属钴是地球上稀缺的元素之一，且具有放射性，其氧化物在电池过充和过放时会与电解液发生剧烈反应，放出大量热量而致使电池起火直至爆炸。因此，钴酸锂和镍钴酸锂的制造成本高，安全性差。锰酸锂虽然较便宜和安全，可是电容量小，而且在高温条件下(55℃以上)的循环使用寿命差。即使经过掺杂和表面化学处理，锰酸锂电池的循环使用寿命仍然无法满足实际要求。因此，锂电池工业，特别是大功率锂电池急需一种成本低廉、环保、容量大和安全的正极材料。
为此，美国德州大学教授J.B.Goodenough等(A.K.Padhi，K.S.Najundaswamy，C.Masgueslier，S.Okada and J.B.Goodenough，J.Eletrochem.Soc.144，1609-1613(1997))于1997年在美国电化学杂志上发表文章，公开了一种新的嵌锂化合物：锂铁磷酸盐多晶体LiFePO4。该晶体中的锂离子电子在FeO6八面体和PO4四面体结构中自由移动，具有锂离子的脱嵌/嵌入可逆性。当1摩尔的锂离子从结构中脱嵌出来时，锂铁磷酸盐多晶体的理论放电容量可达170mAh/g。由于锂、铁储量丰富，锂铁磷酸盐的生产成本低廉。该文预测，由于锂铁磷酸盐材料具有价廉、环保、高性能和安全等特征，其在电池工业中可能具有广阔的应用前景。
但是，锂铁磷酸盐在室温下电导率极低(10-9S/cm)，在正常放电电流(10-1mA/cm2)条件下，锂铁磷酸盐的实际放电容量仅为理论值(170mAh/g)的10％。因此，限制了其在电池中的应用。为了提高锂铁磷酸盐的电导率，近期有文章报道(Suag-Yoon Chang，JasonT.Bloking and Yetming Chiang，Nature，October 123-128(2002))，在其结构中加入微量添加剂，如Mg、Ti、Nb和Zr等，室温下的电导率有了较大提高。但是，该文中提到的添加剂的加入方法复杂，微量元素的价格高，不适合大规模工业生产。此外，锂铁磷酸盐的室温导电空间较大，但其放电电压较低，从而影响了该材料的能量密度。
发明内容
本发明的目的是提供一种以锂铁磷酸盐为基材，还掺有导电掺杂离子和增压掺杂离子的纳米级锂电池正极材料及其制备方法，以克服现有技术存在的上述缺陷。
本发明提供的纳米级锂电池正极材料，该材料以锂铁磷酸盐为基材，还掺有导电掺杂离子和增压掺杂离子，化学通式为：(Lix[M1-x])(Fey[N1-y])PO4，式中：x＝0.9～0.96；y＝0.93～0.97；M为导电掺杂离子，选自Mg2+、Ca2+、Sr2+、Ti2+、Al3+、B3+、Ce3+、C4+、Si4+、Ge4+或P5+其中之一或任意两种以上的组合；N为增压掺杂离子，选自Ti2+、V5+、Co3+、Ni3+、Mn2+、Cr3+、Cu2+或Mo4+其中之一或任意两种以上的组合。
上述纳米级锂电池正极材料的颗粒直径为40～80nm。
本发明还提供了纳米级锂电池正极材料的制备方法，该方法采用固相反应，包括以下步骤：
a.将磷酸二氢锂、乙二酸亚铁、葡萄糖及导电掺杂剂和增压掺杂剂混合均匀后，碎成粉体；
b.将步骤a得到的粉体压粒后，在惰性气体环境中，升温到200～400℃恒温烧结2～3小时；
c.冷却至室温，取出后碎成粉体、混合均匀；
d.将步骤c得到的粉体压粒后，在惰性气体环境中，升温到500～780℃恒温烧结15～20小时；
e.冷却至室温，取出后碎成粉体；
f.将步骤e得到的粉体进行超微气流粉碎和分级。
上述纳米级锂电池正极材料的原料配比：
各原料的摩尔比为：磷酸二氢锂∶乙二酸亚铁∶葡萄糖∶导电掺杂剂∶增压掺杂剂＝1∶0.98～0.99∶0.069～0.07∶0.04～0.1∶0.029～0.07。
所述导电掺杂剂为Mg2+、Ca2+、Sr2+、Ti2+、Al3+、B3+、Ce3+、C4+、Si4+、Ge4+或P5+的化合物或任意两种以上的组合。
所述导电掺杂剂的加入量为：导电掺杂离子的摩尔数是锂离子摩尔数与导电掺杂离子摩尔数之和的4～10％。
所述增压掺杂剂为Ti2+、V5+、Co3+、Ni3+、Mn2+、Cr3+、Cu2+或Mo4+的氧化物、碳酸盐、硫化物或磷酸盐或任意两种以上的组合。
所述增压掺杂剂的加入量为：增压掺杂离子的摩尔数是铁离子摩尔数与增压掺杂离子摩尔数之和的3～7％。
本发明提供的纳米级锂电池正极材料，添加了原子量较小而极化率极高的正离子作为导电掺杂离子，将锂铁磷酸盐正极材料的电导率从3×10-9S/cm提高到1×10-2S/cm，提高了107倍；同时添加增压掺杂离子改变锂铁磷酸盐正极材料晶体结构的化学势能，提高了放电电压(即工作电压)，使其提高了20～25％；另外，该材料的实际放电容量超过250mAh/g；还可以高倍率充、放电，可实现一分钟快速充电，充电寿命超过4000次。该材料不仅可以应用于小容量的锂电池，而且应用在10安以上的大容量、大功率锂电池中更有价值。本发明还提供了上述纳米级锂电池正极材料的制备方法，该方法具有生产成本低、操作方法简单、生产中无污染和成品率高(＞99％)的特点。
附图说明
图1：纳米级锂电池正极材料的扫描电镜图，放大倍数：10,000倍；比例尺：2.0μm。该材料的颗粒直径为40～80nm。
图2：由纳米级锂电池正极材料制成的锂电池充、放电特征曲线图。
图3：纳米级锂电池正极材料的x射线衍射图。
具体实施方式
下面通过具体实施例详细描述本发明的技术方案。
实施例1
第一步，取1000g(9.62摩尔)磷酸二氢锂；1410g(9.80摩尔)乙二酸亚铁；120.5g(0.67摩尔)葡萄糖；导电掺杂剂：17g(0.42摩尔)氧化镁；增压掺杂剂：50g(0.20摩尔)磷酸锰、27g(0.23摩尔)碳酸钴、25g(0.26摩尔)钛酸，放入球磨机中，球磨搅拌混合2小时，碎成粉体；
第二步，将第一步制好的粉体压粒后，放入氧化铝陶瓷坩锅中，于氮气炉中升温至200～300℃，恒温烧结3小时；
第三步，冷却至室温后取出，球磨成粉体、混合均匀；
第四步，将第三步得到的粉体压粒后，在氮气炉中升温至500～600℃，恒温烧结18～20小时，生成掺杂锂铁磷酸盐晶体，自然降至室温；
第五步，将晶体颗粒压碎至粉末状；
第六步，将第五步制备的粉末在超微气流粉碎机上进行破碎和分级，制成纳米级锂电池正极材料，颗粒直径为40～80nm。
经测定，普通锂铁磷酸盐正极材料电导率为3×10-9S/cm，室温放电电压为3.2V；而本实施例提供的纳米级锂电池正极材料的室温电导率和室温放电电压分别为1.30×10-2S/cm和4.0V，分别提高了107倍和25％。
实施例2
第一步，取1000g(9.62摩尔)磷酸二氢锂；1400g(9.73摩尔)乙二酸亚铁；120g(0.67摩尔)葡萄糖；导电掺杂剂：20g(0.32摩尔)硼酸、60g(0.19摩尔)磷酸钙、35g(0.45摩尔)氢氧化铝；增压掺杂剂：30g(0.31摩尔)硫化铜，放入ZrO球磨机中，球磨、搅拌混合2～3小时，碎成粉体；
第二步，将第一步制好的粉体压粒后，放入氧化铝陶瓷坩锅中，于氮气炉中升温至300～400℃，恒温烧结1.5～2.5小时；
第三步，冷却至室温后取出，球磨成粉体、搅拌均匀；
第四步，将第三步得到的粉体压粒后，在氮气炉中继续升温至700～800℃，恒温烧结15～16小时，生成掺杂锂铁磷酸盐晶体，自然降温至室温；
第五步，将晶体颗粒压碎至粉末状；
第六步，将第五步制备的粉末在超微气流粉碎机上进行破碎和分级，制成用于锂电池正极的固体粉体，粉体颗粒直径为40～80nm。
经测定，普通锂铁磷酸盐正极材料电导率为3×10-9S/cm，室温放电电压为3.2V；而本实施例提供的纳米级锂电池正极材料的室温电导率和室温放电电压分别为1.35×10-2S/cm和3.85V，分别提高了107倍和20％。
实施例3
第一步，取1000g(9.62摩尔)磷酸二氢锂；1400g(9.73摩尔)乙二酸亚铁；120g(0.67摩尔)葡萄糖；导电掺杂剂：29g(0.30摩尔)偏钛酸、23g(0.38摩尔)二氧化硅；增压掺杂剂：70g(0.15摩尔)碱式碳酸镍、50g(0.35摩尔)氧化钼，放入ZrO球磨机中球磨、搅拌混合2～3小时，碎成粉体；
第二步，将第一步制好的粉体压粒后，放入氧化铝陶瓷坩锅中，于氮气炉中升温至200～300℃，恒温烧结2～3小时；
第三步，冷却至室温后取出，球磨成粉体、搅拌均匀；
第四步，将第三步得到的粉体压粒后，在氮气炉中继续升温至650～750℃，恒温烧结16～17小时，生成掺杂纳米锂铁磷酸盐晶体，自然降温至室温；
第五步，将晶体颗粒压碎至粉末状；
第六步，将第五步制备的粉末在超微气流粉碎机上进行破碎和分级，制成纳米级锂电池正极材料的固体粉体，颗粒直径为40～80nm。
经测定，普通锂铁磷酸盐正极材料电导率为3×10-9S/cm，室温放电电压为3.2V；而本实施例提供的纳米级锂电池正极材料的室温电导率和室温放电电压分别为1.35×10-2S/cm和3.90V，分别提高了107倍和22％。
本发明实施例1、2和3提供的纳米级锂电池正极材料可以1C～9C的速率快速充、放电。
本发明包括但不限于以上实施例。以上所列具体实施方式仅用于理解本发明的实质，根据现有技术对本发明做出的不脱离本发明实质内容的改变，仍属于本发明的保护范围。
Claims (8)
1.一种纳米级锂电池正极材料，其特征在于：该材料以锂铁磷酸盐为基材，还掺有导电掺杂离子和增压掺杂离子，化学通式为：(Lix[M1-x])(Fey[N1-y])PO4，式中：x＝0.9～0.96；y＝0.93～0.97；M为导电掺杂离子，选自Mg2+、Ca2+、Sr2+、Ti2+、Al3+、B3+、Ce3+、C4+、Si4+、Ge4+或P5+其中之一或任意两种以上的组合；N为增压掺杂离子，选自Ti2+、V5+、Co3+、Ni3+、Mn2+、Cr3+、Cu2+或Mo4+其中之一或任意两种以上的组合。
2.根据权利要求1所述的纳米级锂电池正极材料，其特征在于：该材料的颗粒直径为40～80nm。
3.权利要求1或2所述纳米级锂电池正极材料的制备方法，其特征在于：所述制备方法采用固相反应，包括以下步骤：
a.将磷酸二氢锂、乙二酸亚铁、葡萄糖及导电掺杂剂和增压掺杂剂混合均匀后，碎成粉体，其中，各原料的摩尔比为：磷酸二氢锂∶乙二酸亚铁∶葡萄糖∶导电掺杂剂∶增压掺杂剂＝1∶0.98～0.99∶0.069～0.07∶0.04～0.1∶0.029～0.07；或磷酸二氢锂∶乙二酸亚铁∶葡萄糖∶导电掺杂剂∶增压掺杂剂＝9.62∶9.80∶0.67∶0.42∶0.69；或磷酸二氢锂∶乙二酸亚铁∶葡萄糖∶导电掺杂剂∶增压掺杂剂＝9.62∶9.73∶0.67∶0.96；0.31；或磷酸二氢锂∶乙二酸亚铁∶葡萄糖∶导电掺杂剂∶增压掺杂剂＝9.62∶9.73∶0.67∶0.68∶0.50；
b.将步骤a得到的粉体压粒后，在惰性气体环境中，升温到200～400℃恒温烧结2～3小时；
c.冷却至室温，取出后碎成粉体、混合均匀；
d.将步骤c得到的粉体压粒后，在惰性气体环境中，升温到500～780℃恒温烧结15～20小时；
e.冷却至室温，取出后碎成粉体；
f.将步骤e得到的粉体进行超微气流粉碎和分级。
4.根据权利要求3所述纳米级锂电池正极材料的制备方法，其特征在于：步骤a中，所述导电掺杂剂为Mg2+、Ca2+、Sr2+、Ti2+、Al3+、B3+、Ce3+、C4+、Si4+、Ge4+或P5+的化合物或任意两种以上的组合。
5.根据权利要求3所述纳米级锂电池正极材料的制备方法，其特征在于：步骤a中，所述导电掺杂剂的加入量为：导电掺杂离子的摩尔数是锂离子摩尔数与导电掺杂离子摩尔数之和的4～10％。
6.根据权利要求3所述纳米级锂电池正极材料的制备方法，其特征在于：步骤a中，所述增压掺杂剂为Ti2+、V5+、Co3+、Ni3+、Mn2+、Cr3+、Cu2+或Mo4+的氧化物、碳酸盐、硫化物或磷酸盐或任意两种以上的组合。
7.根据权利要求3所述纳米级锂电池正极材料的制备方法，其特征在于：步骤a中，所述增压掺杂剂的加入量为：增压掺杂离子的摩尔数是铁离子摩尔数与增压掺杂离子摩尔数之和的3～7％。
8.根据权利要求3所述纳米级锂电池正极材料的制备方法，其特征在于：步骤a、c和e中，碎成粉体时，采用ZrO球磨机。
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- 2009-06-23 RU RU2011126090/07A patent/RU2477908C2/ru active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7482097B2 (en) * | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
| CN1457111A (zh) * | 2003-03-18 | 2003-11-19 | 黄穗阳 | 锂电池正极材料及其制备方法 |
| CN1684290A (zh) * | 2004-04-13 | 2005-10-19 | 中国科学院物理研究所 | 一种用于二次锂电池的正极材料和用途 |
| JP2009029670A (ja) * | 2007-07-27 | 2009-02-12 | Kanto Denka Kogyo Co Ltd | オリビン型リン酸鉄リチウム化合物及びその製造方法、並びにオリビン型リン酸鉄リチウム化合物を使用する正極活物質及び非水電解質電池 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107785564A (zh) * | 2017-10-18 | 2018-03-09 | 武汉理工大学 | VTi2.6O7.7纳米颗粒、制备和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2477908C2 (ru) | 2013-03-20 |
| WO2010139125A1 (zh) | 2010-12-09 |
| JP5347031B2 (ja) | 2013-11-20 |
| US20110114899A1 (en) | 2011-05-19 |
| EP2287944B1 (en) | 2016-04-06 |
| AU2009347499B2 (en) | 2012-07-26 |
| EP2287944A1 (en) | 2011-02-23 |
| CN101567449A (zh) | 2009-10-28 |
| AU2009347499A1 (en) | 2010-12-09 |
| EP2287944A4 (en) | 2014-04-23 |
| HK1150096A1 (zh) | 2011-10-28 |
| JP2012510140A (ja) | 2012-04-26 |
| US8470207B2 (en) | 2013-06-25 |
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