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Nonaqueous electrolyte secondary batteries

A non-aqueous electrolyte, secondary battery technology, applied in secondary batteries, battery electrodes, circuits, etc., can solve problems such as low conductivity, reduced reliability and safety of battery systems, and inability to replace LiFePO, and achieve safety. excellent effect

Inactive Publication Date: 2010-02-10
HITACHI LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the LiFePO 4 When used as a positive electrode material, since the management of iron and iron oxide becomes difficult, it is impossible to manage iron that increases the probability of occurrence of internal short-circuit phenomena, and even causes internal short-circuits that cause ignition in the worst case, including manufacturing Reduced reliability and safety of process battery systems
[0009] For this reason, LiMnPO composed of Mn has been carried out 4 The development of Mn in LiMPO 4 (M is at least one or more elements selected from Co, Ni, Mn, and Fe) has the highest Clark number next to Fe, and also has a high operating voltage. However, as shown in Non-Patent Documents 1 and 2 As disclosed in , the olivine-type LiMnPO 4 The conductivity ratio of LiFePO 4 lower, utilizing capacity efficiency with LiFePO 4 The ratio is also quite low, so it cannot be LiFePO 4 substitute
In addition, although it is speculated, the crystal lattice size changes greatly when lithium is detached, causing lattice mismatch, which is also considered to be the cause of low capacity utilization efficiency.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] LiMnPO 4 / C(dextrin)

[0053] 2.675g of LiH 2 PO 4 (manufactured by Aldrich), 4.373 g of MnC 2 o 4 2H 2 O (manufactured by High Purity Chemicals) and 0.826 g of dextrin (manufactured by Wako Pure Chemical Industries) were mixed using a planetary ball mill (manufactured by Fritsch) in which zirconia grinding balls were placed in a zirconia pot, and mixed for 30 minute. This mixed powder was put into an alumina crucible, and under an argon flow of 0.3 L / min, pre-baking was performed at 400° C. for 10 hours. Carry out the first crushing in the agate mortar, put it into the alumina crucible again, under the argon flow of 0.3L / min, carry out formal firing at 700°C for 10 hours, and put the obtained powder in the agate mortar Crushing in medium, and adjusting the particle size with a 45 μm mesh sieve to obtain the desired material.

[0054] Composition analysis was carried out by the ICP method. As a result, Li 1.00 mn 0.98 P 1.02 o 4 Carbon content: 6.1 wt%. The...

Embodiment 2

[0064] LiMn 0.96 Ti 0.03 PO 4 / C(dextrin)

[0065] 2.684g of LiH 2 PO 4 (manufactured by Aldrich), 4.295 g of MnC 2 o 4 2H 2 O (manufactured by Kanto Chemical), 0.213 g of isopropoxytitanium (manufactured by Kanto Chemical), and 0.823 g of dextrin (manufactured by Kanto Chemical) were used as raw materials, synthesized by the same method as in Example 1, and evaluated. The results are put together in Table 1 and Table 2. Here, the utilization capacity up to 4.3 V depends on the content of manganese, but in order to compare the actual capacity, the utilization capacity electric efficiency is the same as that of [Example 1], and was calculated by setting 100% as 170.9 mAh / g.

Embodiment 3

[0067] LiMn 0.95 Ti 0.05 PO 4 / C(dextrin)

[0068] 2.680g of LiH 2 PO 4 (manufactured by Aldrich), 4.252 g of MnC 2 o 4 2H 2 O (manufactured by Kanto Chemical), 0.350 g of isopropoxytitanium (manufactured by Kanto Chemical), and 0.826 g of dextrin (manufactured by Kanto Chemical) were used as raw materials, synthesized by the same method as in Example 1, and evaluated. The results are put together in Table 1 and Table 2.

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Abstract

The present invention is intended to improve load characteristics at the time of charging or discharging by assuring a lithium ion transport pathway in the crystal structure of olivine lithium-containing manganese phosphate. There is used a positive electrode active material which is a composite material comprising a material having an olivine structure and represented by Li1-y[Mn1-xMx]PzO4 (0<x<=0.3, -0.05<=y<1, 0.99<=z<=1.03, and M includes at least one of Li, Mg, Ti, Co, Ni, Zr, Nb, Mo or W) and a carbon material, and which shows an average half width of 0.17 or more, and an intensity ratiobetween a diffraction line near 20 DEG and a diffraction line near 35 DEG of not less than 0.7 and not more than 1.0, in powder X-ray diffractometry.

Description

technical field [0001] The present invention relates to a nonaqueous electrolyte secondary battery having improved load characteristics during charge and discharge. Background technique [0002] Lithium cobaltate has been the mainstream as a positive electrode active material for non-aqueous electrolyte batteries. However, since the production of cobalt as a raw material of lithium cobalt oxide is small and the price is high, the production cost of batteries increases when lithium cobalt oxide is used. In addition, batteries using lithium cobalt oxide have problems in terms of safety when the battery temperature rises. [0003] For this reason, the use of lithium manganate or lithium nickel oxide is currently being studied as a positive electrode active material to replace lithium cobalt oxide. However, lithium manganate cannot achieve sufficient discharge capacity. problems such as dissolution. On the other hand, lithium nickelate has problems such as low discharge volta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/36H01M10/40H01M4/02H01M4/58H01M4/62
CPCH01M4/133Y02E60/122H01M4/5825H01M4/625H01M10/0525H01M4/587H01M4/136H01M4/362Y02E60/10
Inventor 上田笃司远山达哉河野一重
Owner HITACHI LTD