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Cobalt acid lithium battery material adulterated alkaline-earth metal between layers and its preparing method

A technology of alkaline earth metals and battery materials, applied in the fields of alkali metal compounds, battery electrodes, chemical instruments and methods, etc.

Inactive Publication Date: 2006-04-26
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Purpose of the present invention is exactly in order to solve layered LiCoO 2 To solve this problem, a new type of interlayer lithium cobaltate positive electrode material doped with alkaline earth metals for lithium-ion batteries and its molten salt ion exchange reaction preparation method are provided.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020]Lithium hydroxide, basic cobalt carbonate and citric acid are used as raw materials, and the raw materials are weighed and mixed according to the ratio of Li / Co / citric acid=1.1 / 1 / 2.1 (molar ratio), dissolved in deionized water, and formulated as Li + The concentration is 4mol·L -1 The solution was reacted in a rotary evaporator (75°C, 60rpm) for 2h to form a dark red sol, which was then transferred to a vacuum drying oven and dried in vacuum at 120°C for 3h to obtain a fluffy red xerogel. Pretreatment at 500 °C for 3 h to obtain dark brown flocs, after grinding, put them back into the muffle furnace, and roast at 850 °C for 6 h to obtain LiCoO in accordance with the stoichiometric ratio 2 product, as a precursor for molten salt ion exchange reactions.

[0021] Calcium nitrate tetrahydrate Ca(NO 3 ) 2 4H 2 O and layered LiCoO 2 The precursors were mixed according to the ratio of Ca / Li=5 (molar ratio), heated in a water bath at 70°C and continuously stirred for 2 hour...

Embodiment 2

[0023] Lithium hydroxide, basic cobalt carbonate and citric acid are used as raw materials, and the raw materials are weighed and mixed according to the ratio of Li / Co / citric acid=1.15 / 1 / 2.15 (molar ratio), dissolved in deionized water, and formulated as Li + The concentration is 3mol L -1 The solution was reacted in a rotary evaporator (80°C, 60rpm) for 3h to form a deep red sol, which was then transferred to a vacuum drying oven and dried in vacuum at 140°C for 3h to obtain a fluffy red xerogel. Pretreatment at 450°C for 3 hours to obtain dark brown flocs, after grinding, put them back into the muffle furnace, and bake at 900°C for 6 hours to obtain LiCoO in accordance with the stoichiometric ratio 2 product, as a precursor for molten salt ion exchange reactions.

[0024] calcium chloride hexahydrate CaCl 2 ·6H 2 O and layered LiCoO 2 The precursors were mixed according to the ratio of Ca / Li=5 (molar ratio), heated in a water bath at 60°C and continuously stirred for 4 h...

Embodiment 3

[0026] Using the same method as in Example 1 to prepare layered LiCoO 2 Precursor.

[0027] Magnesium nitrate hexahydrate Mg(NO 3 ) 2 ·6H 2 O and layered LiCoO 2 The precursor was weighed and mixed according to the ratio of Mg / Li=15 (molar ratio), heated in an oil bath at 120°C and stirred continuously for 4 hours, filtered under reduced pressure and washed with acetone three times, and the filter cake was vacuum-dried at 90°C for 3 hours , and then roasted at 400°C for 15h to obtain the product of the present invention. ICP and XRD tests show that the product is composed of Li 0.95 Mg 0.025 CoO 2 , belongs to the hexagonal crystal system, the electrochemical test results are shown in Table 1.

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PUM

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Abstract

The invention relates to a new anode material with interlaminar doping Li(1-2beta)(AE) (beta)CoO2 (AEú¢Mgú¼Ca) by substituting lithium ion by alkaline-earth metal ion and opposite fused salt ion exchange reaction preparation method. Wherein, the preparation method comprises: preparing layer-shape LiCoO2 predecessor with little and even size with citrate sol-gel method; substituting part lithium ion with Mg2+ or Ca2+ by fused salt ion exchange reaction; baking to distribute lithium ion and alkaline-earth metal ion evenly in main body layer constructed by CoO2. This product has more stable structure, better anti-overcharge performance, higher specific capacity and super electrochemical circulation property.

Description

technical field [0001] The invention relates to a lithium cobaltate battery material doped with alkaline earth metal between layers and a preparation method thereof, belonging to the technical field of lithium ion battery materials and its preparation. Background technique [0002] With α-NaFeO 2 type layered LiCoO 2 It has the most excellent electrochemical performance among various lithium-ion battery cathode materials, and is the main cathode material for commercial lithium-ion batteries. But LiCoO 2 Expensive, the actual specific capacity is 120~140mAh·g -1 , only its theoretical capacity (274mAh·g -1 ) about 50%; LiCoO 2 The anti-overcharge performance is poor, and the specific capacity decreases rapidly at a higher charging voltage. To overcome LiCoO 2 Existing problems, people have studied and adopted a variety of modification measures and methods. [0003] At present, the most researched modification method is to use Ni, Al, Ti, Fe and other elements to dope ...

Claims

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Application Information

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IPC IPC(8): C01D15/00C01G51/00H01M4/525H01M4/62
CPCY02E60/10
Inventor 杨文胜段雪李秀梅
Owner BEIJING UNIV OF CHEM TECH
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