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Lithium zirconium titanate-carbon lithium ion battery negative electrode material and preparation method thereof

A carbon negative electrode material and lithium-ion battery technology, applied in battery electrodes, negative electrodes, secondary batteries, etc., can solve the problems of small specific gravity, fast attenuation, and low volumetric energy density of nanomaterials

Inactive Publication Date: 2018-11-23
ZHEJIANG FOLTA TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The material is fired under Ar atmosphere at 750 degrees. The material is actually coated with carbon. Since carbon is amorphous carbon, the conductivity of the material is not ideal, and the stability is poor.
Other vanadium-containing negative electrode materials include carbon-coated Li 3 VO 4 Materials and the carbon-coated Li disclosed in CN20130237355.8 3 VO 4 materials, all have poor conductivity of amorphous carbon, and the nano-carbon coating layer is due to Li 3 VO 4 The volume expansion of the material leads to the destruction of the cladding layer, and the Li 3 VO 4 The material particles are in contact with each other, the conductivity becomes poor, and the charge and discharge capacity of the material decreases
[0005] Li 2 MoO 4 and Li 2 WO 4 with Li 3 VO 4 Similar to Li 2 MoO 4 (capacity of 769mAh / g when transporting 5 electrons and 5 lithium ions) and Li 2 WO 4 (When transporting 5 electrons and 5 lithium ions, the capacity is 510mAh / g) are potential high-capacity negative electrode materials, but due to the poor conductivity of these materials, they cannot be charged quickly, and the first charge and discharge efficiency is low and the decay is fast. , so it cannot be directly used as electrode material
Yanming Zhao (Electrochimica Acta 174 (2015) 315-326) and (X. Liu, Y. Zhao, Y. Lyu, Z. Zhang, H. Li, Y. Hu, Z. Wang, Q. Kuang, Y. Dong , Z.Liang, Q.Fan and L.Chen, Nanoscale, 2014, DOI: 10.1039 / C4NR04226C.) reported Li 2 MoO 4 Nanorod and nanotube anode materials, the first charge and discharge efficiency is only about 30%, the stable capacity is lower than 200mAh / g and decays quickly, after the Li is coated with carbon generated by the decomposition of organic matter 2 MoO 4 Nanorod and nanotube anode materials will perform better, with a capacity of 670mAh / g and an initial charge and discharge efficiency of about 64%, but they still decay quickly. On the one hand, the carbon generated by the decomposition of organic matter at low temperature is amorphous carbon. The electrical conductivity and the first charge and discharge efficiency of itself are poor. In addition, because the coated carbon layer is too thin, it is easy to destroy the carbon coating layer and destroy the Li when the volume changes. 2 MoO 4 nanorods and nanotubes, making Li 2 MoO 4 Nanorods and nanotubes agglomerate into non-conductive inorganic salts and lose activity
, although the weight capacity of the material seems to be very high (670mAh / g), the specific gravity of nanomaterials is small and the volumetric energy density (capacity) is very low, which has no practical value

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] [Li 2 TiO 3 ] x [Li 2 ZrO 3 ] 1-x -carbon

[0033] Preparation of composite material: Weigh 0.3200 g of Li 2 TiO 3 (homemade), 4.7200 g Li 2 ZrO 3 (self-made), 6.200 grams of graphite (particle size less than 20 microns), 4.000 grams of polyvinyl alcohol in a 250ml ball mill jar, add 100ml deionized water and an appropriate amount of zirconium beads, and ball mill for 4h at a speed of 300r / min. The mixed material was spray-dried to obtain a powder sample, and then heated at 450 °C for 4 h under the protection of Ar gas to obtain [Li 2 TiO 3 ] x [Li 2 ZrO 3 ] 1-x - Carbon composite material.

[0034] The above materials, PVDF (3% PVDF in N-methylpyrrolidone solution), and conductive carbon black were mixed at a mass ratio of 8:1:1 to prepare a slurry. Apply the slurry on the copper foil, and then dry it in nitrogen at 150°C for 2 hours, use the prepared electrode as the positive electrode, use the metal Li sheet as the negative electrode, and use 1.0M LiP...

Embodiment 2

[0036] Preparation of composite material: Weigh 3.100 grams of Li 2 TiO 3 , 1.840 g Li 2 ZrO 3 , 6.000 grams of graphite (particle size less than 20 microns), 2.000 grams of polyethylene glycol in a 250ml ball mill jar, add 100ml deionized water and an appropriate amount of zirconium beads, ball mill for 4 hours at a speed of 300r / min, and mix the material Spray-dried to obtain a powder sample, and then heated at 400 °C for 4 h under the protection of Ar gas to obtain [Li 2 TiO 3 ] x [Li 2 ZrO 3 ] 1-x - Carbon composite material.

[0037] The above materials, PVDF (3% PVDF in N-methylpyrrolidone solution), and conductive carbon black were mixed at a mass ratio of 8:1:1 to prepare a slurry. Apply the slurry on the copper foil, and then dry it in nitrogen at 150°C for 2 hours, use the prepared electrode as the positive electrode, use the metal Li sheet as the negative electrode, and use 1.0M LiPF 6 Carbonate solution was used as the electrolyte to make half-cells. Cha...

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PUM

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Abstract

The invention discloses a lithium zirconium titanate-carbon ([Li2TiO3]x[Li2ZrO3]1-x-carbon lithium ion battery negative electrode material and a preparation method thereof, wherein x is number of 0.01-0.99. By adopting a dispersing agent, ([Li2TiO3]x[Li2ZrO3]1-x and carbon are in full contact to prepare the lithium battery negative electrode material with high conductivity, high charge-discharge current density, high charge-discharge cycle stability and high capacity.

Description

technical field [0001] The invention relates to a high-capacity lithium-ion battery negative electrode material and a preparation method thereof; more particularly, the invention relates to a lithium-titanate-zirconate-carbon composite electrode material for a lithium-ion battery and a preparation method thereof. Background technique [0002] At present, due to the high Coulomb capacity of carbon materials (graphite theoretical value 372mAh / g, actual value 300-350mAh / g), lower production cost and longer cycle life [Wu, Y.P.; Rahm, E.; Holze, R. Carbon AnodeMaterials for Lithium Ion Batteries. J. Power Sources 2003, 114, 228; Marom, R.; Amalraj, S.F.; Leifer, N.; Jacob, D.; .Mater.Chem.2011, 21, 9938], lithium-ion batteries generally use hard carbon, soft carbon and graphite as negative electrode materials. However, due to the low crystallinity of hard carbon and soft carbon, although it can be charged quickly, it is difficult to use on a large scale due to the low Coulomb c...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/485H01M4/62H01M10/0525
CPCH01M4/364H01M4/485H01M4/625H01M10/0525H01M2004/027Y02E60/10
Inventor 杨颉何婉芳其他发明人请求不公开姓名
Owner ZHEJIANG FOLTA TECH CO LTD