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Preparation method and application of a spinel structure and layered structure cobalt-free composite material

A spinel structure and layered structure technology, applied in structural parts, positive electrodes, active material electrodes, etc., can solve problems such as difficulty in meeting the use requirements of new energy vehicles, high residual alkali content on the surface, and reduced interface bonding force, etc. Achieve the effect of improving battery safety performance, reducing residual alkali on the surface, and inhibiting cycle life

Active Publication Date: 2021-11-26
TIANJIN B&M SCI & TECH
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Problems solved by technology

Therefore, conventional cobalt-free ternary materials are difficult to meet the requirements of new energy vehicles, and it is necessary to improve the rate performance of the material and suppress the residual alkali of the material.
[0004] For lithium-ion batteries, the essence of the electrochemical reaction is the interface reaction first, and then the deintercalation of lithium ions. The interface reaction is more difficult and is the bottleneck of the electrochemical reaction. In order to improve the rate performance of cobalt-free materials, it can be used in Its surface is covered with a layer of fast ion conductors, but the fast ion conductors are mostly electrochemically inert substances, which will reduce the specific capacity of the material
[0005] In addition, because cobalt-free materials do not have the support of the layered structure of Co, the lithium on the surface is easy to precipitate, resulting in a high content of residual alkali on the surface, and lithium carbonate in the residual alkali will decompose under high pressure to generate carbon dioxide, and the residual alkali on the surface The content is relatively high, so it is necessary to reduce the surface residual alkali of this type of material
Metal oxide coating is a common method to reduce the residual alkali on the surface of lithium-ion battery cathode materials, but when the coating temperature is too high, the interface will be inert, the specific capacity will decrease, the DCR will increase, and the rate performance will deteriorate; when the temperature is too low, Reduced interfacial bonding force and poor cycle performance

Method used

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  • Preparation method and application of a spinel structure and layered structure cobalt-free composite material
  • Preparation method and application of a spinel structure and layered structure cobalt-free composite material
  • Preparation method and application of a spinel structure and layered structure cobalt-free composite material

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preparation example Construction

[0032] Such as figure 1 As shown, the invention provides a method for preparing a spinel structure and a layered structure cobalt-free composite material, comprising the steps of:

[0033] 1) In terms of element molar ratio, take manganese source and nickel source with Mn:Ni=1:3, mix them with deionized water and add them into a sand mill for grinding to obtain slurry I, the particle size of slurry I is D 50 ≤0.1μm;

[0034] 2) The ternary precursor Ni x mn (1-x) (OH) 2 Add to the above-mentioned slurry I and mix evenly to obtain slurry II, wherein Ni x mn (1-x) (OH) 2 Amount of substance / (amount of manganese substance+nickel substance in slurry I)=(98.5~99.5):1;

[0035] 3) Spray drying the slurry II to obtain the material III, and the spray drying temperature is 250-450°C;

[0036] 4) Mix the material III and lithium hydroxide uniformly in a high-speed mixer to obtain material IV, wherein the amount of lithium hydroxide substance=(1.02~1.04)*(amount of manganese subs...

Embodiment 1

[0050] A method for preparing a spinel structure and a layered structure cobalt-free composite material, comprising the steps of:

[0051] 1) Weigh manganese carbonate, nickel hydroxide, and deionized water according to the amount ratio of nickel to manganese to 1:3, and add them into a sand mill for grinding to obtain slurry I and slurry particle size D 50 = 0.08 μm;

[0052] 2) The ternary precursor Ni 0.75 mn 0.25 (OH) 2 Add to the above-mentioned slurry I and mix evenly to obtain slurry II, wherein Ni 0.75 mn 0.25 (OH) 2 The amount of substance / (the amount of manganese substance+the amount of nickel substance in slurry I)=98.5:1;

[0053] 3) Spray-dry the above-mentioned slurry II to obtain material III, and the spray-drying temperature is 250° C.;

[0054] 4) Mix the above-mentioned material III and lithium hydroxide uniformly in a high-speed mixer to obtain material IV, wherein the amount of lithium hydroxide substance=1.02*(the amount of manganese substance in sl...

Embodiment 2

[0066] A method for preparing a spinel structure and a layered structure cobalt-free composite material, comprising the steps of:

[0067] 1) Weigh manganese trioxide, nickel hydroxide, and deionized water according to the amount ratio of nickel to manganese to 1:3, and add them into a sand mill for grinding to obtain slurry I and slurry particle size D 50 = 0.06 μm;

[0068] 2) The ternary precursor Ni 0.8 mn 0.2 (OH) 2 Add to the above-mentioned slurry I and mix evenly to obtain slurry II, wherein Ni 0.8 mn 0.2 (OH) 2 The amount of substance / (the amount of manganese substance+nickel substance in slurry I)=99.5:1;

[0069] 3) Spray-dry the above-mentioned slurry II to obtain material III, and the spray-drying temperature is 300° C.;

[0070] 4) Mix the above-mentioned material III and lithium hydroxide uniformly in a high-speed mixer to obtain material IV, wherein the amount of lithium hydroxide substance=1.04*(the amount of manganese substance in slurry I+the amount o...

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Abstract

The invention discloses a method for preparing a cobalt-free composite material with a spinel structure and a layered structure. It includes the following steps: first, a layer of 5V spinel nickel-manganese material is coated on the surface of the cobalt-free ternary material through sand grinding, spray drying and high temperature processes, and then the outermost layer is compound coated with glass through the low temperature coating process. Properties of substances and metal oxides. In the present invention, by adding vitreous substance and oxide composite coating, utilizing the meltability of vitreous substance at low temperature, the binding force with oxide and ternary material is improved at low temperature, and at the same time, a higher specific capacity is ensured.

Description

technical field [0001] The invention relates to the field of cathode materials for lithium-ion secondary batteries, in particular to a preparation method and application of a cobalt-free composite material with a spinel structure and a layered structure. Background technique [0002] The promotion and application of new energy vehicles is imperative, among which the power source lithium-ion battery is the core part of new energy vehicles, and the positive electrode material in the lithium-ion battery system is the decisive factor. In the existing cathode material system, ternary materials have the advantages of high specific energy density and good cycle performance, and are the mainstream materials for new energy vehicles. [0003] However, the global reserves of cobalt, the main raw material used in ternary materials, are relatively low, and it is difficult to meet the rapid development of new energy vehicles. Therefore, the overall development trend of ternary materials i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/62H01M4/505H01M4/525H01M10/0525
CPCH01M4/505H01M4/525H01M4/628H01M10/0525H01M2004/021H01M2004/028Y02E60/10
Inventor 宋英杰吕菲伏萍萍徐宁吴孟涛
Owner TIANJIN B&M SCI & TECH
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