Lithium ion battery anode material adopting in-situ developed heterogeneous core-shell structure and preparation method of material

A lithium-ion battery, core-shell structure technology, applied in battery electrodes, secondary batteries, structural parts, etc., can solve the problem of unfavorable formation of two-phase composite materials with a stable core-shell structure, different proportions of transition metal elements, and different core layers and shell problems, to achieve the effect of improving the first-time efficiency, large capacity, and good batch stability

Active Publication Date: 2016-04-20
TIANJIN UNIVERSITY OF TECHNOLOGY
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Problems solved by technology

Adv.Mater.,2013,25:3722 reported a method of coating spinel materials on the surface of lithium-rich layered materials: first, the surface of lithium-rich layered materials is coated with a layer of manganese salt, and then co-fused by roasting A method for forming a spinel phase on the surface and then preparing a spinel-coated lithium-rich layered material, but the transition between the spinel phase and the lithium-rich layered phase of the composite material prepared by this method Different proportions of metal elements are not conducive to the formation of a two-phase composite material with a stable structure and a controllable thickness of the core-shell structure
Phys.Chem.Chem.Phys., 2015, 17:1257 also proposed a method for coating lithium-rich layered materials with spinel phase: ac...

Method used

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  • Lithium ion battery anode material adopting in-situ developed heterogeneous core-shell structure and preparation method of material
  • Lithium ion battery anode material adopting in-situ developed heterogeneous core-shell structure and preparation method of material
  • Lithium ion battery anode material adopting in-situ developed heterogeneous core-shell structure and preparation method of material

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Preparation of lithium-rich layered phase material Li 1.5 Ni 0.15 mn 0.65 co 0.2 o 2.5 Heterogeneous spinel phase material Li 0.5 Ni 0.15 mn 0.65 co 0.2 o 2 Lithium-ion battery cathode material with a core-shell structure of the shell 0.9[Li 1.5 Ni 0.15 mn 0.65 co 0.2 o 2.5 ]·0.1[Li 0.5 Ni 0.15 mn 0.65 co 0.2 o 2 ] (x takes 0.9, a takes 0.1, M is Co);

[0034] 1) Weigh 394.3gNiSO 4 ·6H 2 O, 1098.6gMnSO 4 ·H 2 O and 562.2gCoSO 4 ·7H 2 O preparation metal ion total concentration is the mixed salt solution 5L of 2mol / L, obtains reaction solution A;

[0035] 2) Under continuous stirring conditions, slowly add the following reaction solution B to the above reaction solution A 1 , for co-precipitation reaction.

[0036] Reaction solution B 1 : A mixed solution of ammonia water and sodium carbonate, wherein the concentration of ammonia water is 0.2mol / L, and the concentration of sodium carbonate is 2mol / L.

[0037] By adjusting the reaction solution...

Embodiment 2

[0045] Preparation of lithium-rich layered phase material Li 1.5 Ni 0.2 mn 0.7 Cr 0.1 o 2.5 Heterogeneous spinel phase material Li 0.5 Ni 0.2 mn 0.7 Cr 0.1 o 2 Lithium-ion battery cathode material with a core-shell structure of the shell 0.7[Li 1.5 Ni 0.20 mn 0.70 Cr 0.10 o 2.5 ]·0.3[Li 0.5 Ni 0.2 mn 0.7 Cr 0.10 o 2 ] (x gets 0.7, a gets 0.05, M is Cr);

[0046] 1) Weigh 237.7g NiCl respectively 2 ·6H 2 O, 591.6gMnSO 4 ·H 2 O, 200.1gCr(NO 3 ) 3 9H 2 O preparation metal ion total concentration is 10L of the mixed salt solution of 0.5mol / L, obtains reaction solution A;

[0047] 2) Under continuous stirring conditions, slowly add the following reaction solution B to the above reaction solution A 1 , for co-precipitation reaction.

[0048] Reaction solution B 1 : A mixed solution of ammonia water and sodium carbonate, wherein the concentration of ammonia water is 0.2mol / L, and the concentration of sodium carbonate is 3mol / L;

[0049] By adjusting the rea...

Embodiment 3

[0057] Preparation of lithium-rich layered phase material Li 1.5 Ni 0.20 mn 0.70 Fe 0.03 al 0.07 o 2.5 Heterogeneous spinel phase material Li 0.5 Ni 0.2 mn 0.7 Fe 0.03 al 0.07 o 2 Lithium-ion battery cathode material with a core-shell structure of the shell 0.8[Li 1.5 Ni 0.20 mn 0.70 Fe 0.03 al 0.07 o 2.5 ]·0.2[Li 0.5 Ni 0.2 mn 0.7 Fe 0.03 al 0.07 o 2 ] (x is 0.8, a is 0.05, M is a mixture of Fe and Al, wherein the ratio of Fe and Al is 3:7);

[0058] 1) Weigh 497.7gNi(CH 3 COO) 2 4H 2 O, 1183.1gMnSO 4 ·H 2 O,81.1gFeCl 3 ·6H 2 O and 262.6gAl(NO 3 ) 3 9H 2 O preparation metal ion total concentration is the mixed salt solution 2L of 5mol / L, obtains reaction solution A;

[0059] 2) Under continuous stirring conditions, slowly add the following reaction solution B to the above reaction solution A 1 , for co-precipitation reaction.

[0060] Reaction solution B 1 : A mixed solution of ammonia water and sodium carbonate, wherein the concentration of...

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Abstract

The invention provides a lithium ion battery anode material adopting an in-situ developed heterogeneous core-shell structure and a preparation method of the material. The lithium ion battery anode material is a composite with a lithium-rich lamellar phase material as a core layer and a heterogeneous spinel phase generated on the surface of the core layer in an in-situ manner. The lithium ion battery anode material is prepared in the steps as follows the lithium-rich lamellar phase material containing Ni, Mn and M is prepared from carbonate or hydroxides with a coprecipitation method and then dispersed in a mixed salt solution of Ni, Mn and M, the amount-of-substance ratio of Ni to Mn to M in the solution is the same with that in the lithium-rich lamellar phase material, the coprecipitation reaction is performed again, and the mixed metal carbonate (or metal hydroxide) coated lithium-rich lamellar phase material is obtained, the lithium-rich lamellar phase material is sintered at the high temperature in the absence of a Li source, and the lithium ion battery anode material adopting the in-situ developed heterogeneous core-shell structure can be obtained. The lithium ion battery anode material adopting the in-situ developed heterogeneous core-shell structure has the advantages as follows the shell layer coats the core layer in a uniform, complete and thickness-controllable manner, no obvious phase boundaries exist between the core layer and the shell layer, and the electrochemical performance of the material is improved.

Description

technical field [0001] The invention belongs to the technical field of lithium-ion battery cathode materials, in particular to a preparation method of a lithium-ion battery cathode material with a core-shell structure. Background technique [0002] At present, lithium-ion batteries have been widely used in various mobile appliances, such as mobile phones, cameras, and notebook computers. Cathode materials are an important part of lithium-ion batteries, and the development of high-energy-density cathode materials for lithium-ion batteries has become a research hotspot. [0003] Composite materials of layered Li-rich layered phases and spinel phases have been extensively studied in recent years. J.PowerSources,2013,240:193. reported a method for preparing lithium-rich layered phase and spinel phase composite materials: first prepare the hydroxide co-precipitation precursor of Ni and Mn, and then mix It is mixed and roasted with lithium salt to obtain a composite material wit...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/485H01M4/505H01M4/525H01M4/58H01M10/0525B82Y30/00B82Y40/00
CPCB82Y30/00B82Y40/00H01M4/366H01M4/485H01M4/505H01M4/525H01M4/5825H01M10/0525Y02E60/10
Inventor 张联齐马春龙张洪周
Owner TIANJIN UNIVERSITY OF TECHNOLOGY
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