CN112301271A - Carbon-oxide electrolyte coated battery negative electrode material and preparation method thereof - Google Patents

Carbon-oxide electrolyte coated battery negative electrode material and preparation method thereof Download PDF

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CN112301271A
CN112301271A CN201910925563.4A CN201910925563A CN112301271A CN 112301271 A CN112301271 A CN 112301271A CN 201910925563 A CN201910925563 A CN 201910925563A CN 112301271 A CN112301271 A CN 112301271A
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carbon
oxide electrolyte
negative electrode
electrode material
coated
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谭迎宾
李铮铮
王婧洁
杨兵
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to PCT/CN2020/117016 priority Critical patent/WO2021057765A1/en
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Abstract

The invention discloses a battery cathode material coated by a carbon-oxide electrolyte, which comprises the following components: the battery negative electrode material of the core part is coated with a carbon-oxide electrolyte layer. In addition, the invention also discloses a preparation method of the battery negative electrode material coated by the carbon-oxide electrolyte, which comprises the following steps: mixing a battery negative electrode material, a carbon source organic matter and nano-scale oxide electrolyte particles through ball milling; and then high-temperature calcination is carried out to obtain the battery negative electrode material coated by the carbon-oxide electrolyte. The battery cathode material can overcome the defects of the prior art, has higher conductivity and lithium ion conductivity, and can show high discharge capacity, perfect rate performance and long cycle performance when being applied to a solid-state lithium ion battery cathode.

Description

Carbon-oxide electrolyte coated battery negative electrode material and preparation method thereof
Technical Field
The invention relates to a battery material and a preparation method thereof, in particular to a battery cathode material and a preparation method thereof.
Background
At present, the energy problem is increasingly prominent, and the development and utilization of novel energy storage devices become important research points. Lithium ion batteries have the advantages of high specific energy, long cycle life, environmental friendliness, and the like, and have been widely used in the fields of electronic devices, electric vehicles, and the like.
However, the conventional lithium ion battery generally adopts an organic liquid electrolyte, and the organic liquid electrolyte of the system is flammable and explosive, so that serious potential safety hazard is brought to the battery. In order to solve the safety problem, solid-state batteries have come to be produced, which solve the safety problem of batteries by using solid-state electrolytes instead of conventional organic electrolytes, however, the current conductivity and discharge capacity of the negative electrode materials are increasingly difficult to meet the current use requirements.
Based on this, it is desirable to obtain a battery negative electrode material that can overcome the disadvantages of the prior art, has high electrical conductivity and lithium ion conductivity, and can exhibit high discharge capacity, perfect rate performance and long cycle performance when applied to a solid state lithium ion battery negative electrode.
Disclosure of Invention
An object of the present invention is to provide a carbon-oxide electrolyte-coated battery negative electrode material which can overcome the disadvantages of the prior art, has high conductivity and lithium ion conductivity, and can exhibit high discharge capacity, perfect rate performance, and long cycle performance when applied to a solid-state lithium ion battery negative electrode.
In order to achieve the above object, the present invention provides a carbon-oxide electrolyte-coated battery anode material comprising: the battery negative electrode material of the core part is coated with a carbon-oxide electrolyte layer.
Further, in the carbon-oxide electrolyte-coated battery negative electrode material according to the present invention, the battery negative electrode material includes: at least one of silicon carbon, graphite, soft carbon, and hard carbon.
Further, in the carbon-oxide electrolyte-coated battery anode material according to the present invention, the oxide electrolyte in the carbon-oxide electrolyte layer includes: li7La3Zr2O12，0.2Al-Li7La3Zr2O12，Ba-Sb-Li7La3Zr2O12，Ge-Li7La3Zr2O12，Li6.75La3Zr1.75Ta0.25O12，Li6.75La3Zr1.75Nb0.25O12At least one of (a).
In the technical solution of the present invention, Li is7La3Zr2O12Hereinafter referred to as LLZO, 0.2Al-Li7La3Zr2O12Hereinafter abbreviated as LLZAO, Li6.75La3Zr1.75Ta0.25O12Hereinafter referred to as LLZTO, Li6.75La3Zr1.75Nb0.25O12Hereinafter referred to as LLZNO.
Accordingly, another object of the present invention is to provide a method for preparing the above carbon-oxide electrolyte coated battery negative electrode material, wherein the battery negative electrode material obtained by the preparation method has high conductivity and lithium ion conductivity.
In order to achieve the above object, the present invention provides a method for preparing the above carbon-oxide electrolyte coated battery anode material, comprising the steps of:
mixing a battery negative electrode material, a carbon source organic matter and nano-scale oxide electrolyte particles through ball milling; and then high-temperature calcination is carried out to obtain the battery negative electrode material coated by the carbon-oxide electrolyte.
Further, in the preparation method of the present invention, the carbon source organic matter comprises: at least one of polyethylene oxide, polyethylene glycol, sucrose, glucose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, polyacrylate, polyurethane, cellulose, starch, amino acid, melamine, dicyandiamide, phenolic resin and epoxy resin.
Further, in the production method of the present invention, the size of the oxide electrolyte particle is 500nm or less.
Further, in the preparation method of the invention, the technological parameters for ball milling meet at least one of the following conditions:
the ball milling speed is 100-;
the ball milling time is 1-24 h;
the ball-material ratio is 1-100.
In the technical scheme of the invention, the pellet-to-feed ratio refers to the mass ratio of the mass of the pellets to the total mass of the battery negative electrode material, the carbon source organic matter and the nano-scale oxide electrolyte particles.
Further, in the preparation method of the invention, the calcination temperature is 500-900 ℃.
Further, in the preparation method of the present invention, the atmosphere of the calcination protection is at least one of nitrogen, argon, helium and ammonia.
Further, in the preparation method, the calcining step comprises raising the temperature to the calcining temperature at the speed of 0.5-20 ℃/min and preserving the temperature for 0.5-6 h.
Further, in the preparation method, the battery negative electrode material, the carbon source organic matter and the oxide electrolyte particles are mixed according to the mass part ratio of (70-95) to (5-20) to (5-15).
Compared with the prior art, the battery cathode material coated by the carbon-oxide electrolyte and the preparation method thereof have the advantages and beneficial effects as follows:
the battery cathode material coated by the carbon-oxide electrolyte can accurately control the contents of the carbon-oxide electrolyte and carbon, so that large-scale production can be realized. In addition, the battery cathode material coated with the carbon-oxide electrolyte is synthesized by adopting an organic matter and oxide solid electrolyte calcining process to obtain the battery cathode material coated with the carbon-solid electrolyte, wherein the carbon coating can effectively improve the conductivity of the silicon-carbon material, and the solid electrolyte can effectively improve the lithium ion conductivity of the silicon-carbon material, so that the impedance and the polarization degree are effectively reduced, and the purpose of improving the electrochemical performance of the lithium battery is realized.
In addition, the battery negative electrode material contains heteroatoms such as N, S, P element due to the carbon-oxide electrolyte, so that the conductivity of the battery negative electrode material can be improved, and an additional chemical site can be provided for lithium ions, thereby improving the lithium storage performance of the lithium battery.
In addition, the preparation method of the invention also has the advantages and beneficial effects.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon-oxide electrolyte coated battery anode material of example 1;
fig. 2 is a graph of the electrochemical performance of the carbon-oxide electrolyte coated battery anode material of example 2;
fig. 3 is a graph of the electrochemical performance of the carbon-oxide electrolyte coated battery anode material of example 3.
Detailed Description
The carbon-oxide electrolyte coated battery negative electrode material and the preparation method thereof according to the present invention will be further explained and illustrated with reference to the following specific examples and drawings of the specification, but the explanation and the illustration should not be construed as an undue limitation on the technical solution of the present invention.
Example 1
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing a silicon-carbon material, polyethylene oxide serving as carbon source organic matter and nano-grade oxide electrolyte LLZO particles according to a ratio of 80:10:10, adding zirconia balls with the mass being 5 times of that of the mixture, and performing ball milling for 2 hours at a rotating speed of 300 per minute. And putting the obtained powder into a tubular furnace in a nitrogen atmosphere, heating to 700 ℃ at a heating rate of 5 ℃ per minute, and preserving heat for 2 hours to obtain the battery cathode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
Fig. 1 is a scanning electron micrograph of the carbon-oxide electrolyte coated battery anode material of example 1.
As shown in fig. 1, in the carbon-oxide electrolyte-coated battery anode material of example 1, the battery anode material as the core portion was coated with a carbon-oxide electrolyte layer.
Example 2
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing a silicon-carbon material, glucose serving as carbon source organic matter and nano-grade oxide electrolyte LLZTO particles according to a ratio of 80:5:15, adding zirconia balls with the mass being 2 times of that of the mixture, and performing ball milling for 6 hours at 350 rotating speed per minute. And putting the obtained powder into a tubular furnace in an argon atmosphere, heating to 750 ℃ at the temperature rise rate of 10 ℃ per minute, and preserving the temperature for 1 hour to obtain the battery negative electrode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
Fig. 2 is a graph of the electrochemical performance of the carbon-oxide electrolyte coated battery anode material of example 2.
As shown in fig. 2, the carbon-oxide electrolyte coated battery negative electrode material of example 2 was measured at 0.1C (1C 600mAh g)-1) The capacity can be kept at 579mAh g after 50 times of circulation under the current density-1。
Example 3
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing a silicon-carbon material, melamine serving as carbon source organic matter and nano-grade oxide electrolyte LLZAO particles according to a ratio of 75:10:15, adding zirconia balls with the mass being 4 times of that of the silicon-carbon material, and performing ball milling for 3 hours at a rotating speed of 500 per minute. And putting the obtained powder into a tubular furnace in helium atmosphere, heating to 650 ℃ at the temperature rise rate of 2 ℃ per minute, and preserving heat for 4 hours to obtain the battery cathode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
Fig. 3 is a graph of the electrochemical performance of the carbon-oxide electrolyte coated battery anode material of example 3.
As shown in fig. 3, the carbon-oxide electrolyte coated battery negative electrode material of example 3 can maintain a capacity of 548mAh g after 80 cycles at a current density of 0.2C-1. The coulombic efficiencies are all more than 99.5%.
Example 4
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing a silicon-carbon material, phenolic resin serving as an organic carbon source and nano-grade oxide electrolyte LLZNO particles according to a ratio of 75:15:10, adding zirconia balls with the mass being 2 times of that of the mixture, and performing ball milling for 12 hours at a rotating speed of 250 per minute. And putting the obtained powder into a tubular furnace in an ammonia atmosphere, heating to 600 ℃ at the temperature rise rate of 2 ℃ per minute, and preserving the temperature for 6 hours to obtain the battery cathode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
Example 5
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing silicon-carbon material, starch as carbon source organic matter and nanometer level oxide electrolyte LLZTO particles in a ratio of 90:5:5, adding zirconia balls with 2 times of mass, and ball-milling at 450 rotation speed per minute for 2 hours. And putting the obtained powder into a tubular furnace in an ammonia atmosphere, heating to 800 ℃ at the temperature rise rate of 15 ℃ per minute, and preserving the temperature for 1 hour to obtain the battery cathode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
Example 6
In the present embodiment, the method for preparing the carbon-oxide electrolyte-coated battery anode material is specifically as follows:
mixing a silicon-carbon material, polyacrylate serving as carbon source organic matter and nano-grade oxide electrolyte LLZNO particles according to a ratio of 85:5:10, adding zirconia balls with the mass being 10 times of that of the mixture, and performing ball milling for 2 hours at a rotating speed of 300 per minute. And putting the obtained powder into a tubular furnace in an argon atmosphere, heating to 650 ℃ at the temperature rise rate of 5 ℃ per minute, and preserving the temperature for 3 hours to obtain the battery cathode material coated with the carbon-oxide electrolyte.
In the present embodiment, the oxide electrolyte particles are 500nm or less.
In addition, in the above embodiments, the battery negative electrode material is a silicon carbon material, but in some other embodiments, the battery negative electrode material may further include at least one of silicon carbon, graphite, soft carbon, and hard carbon.
In addition, in the technical solution of the present invention, the carbon source organic substance may further include at least one of polyethylene glycol, sucrose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, polyurethane, cellulose, amino acid, dicyandiamide, and epoxy resin, besides those shown in the above examples.
In addition, the oxide electrolyte may further include Ba-Sb-Li7La3Zr2O12，Ge-Li7La3Zr2O12At least one of (a).
In conclusion, the battery cathode material coated with the carbon-oxide electrolyte can accurately control the contents of the carbon-oxide electrolyte and carbon, so that large-scale production can be realized. In addition, the battery cathode material coated with the carbon-oxide electrolyte is synthesized by adopting an organic matter and oxide solid electrolyte calcining process to obtain the battery cathode material coated with the carbon-solid electrolyte, wherein the carbon coating can effectively improve the conductivity of the silicon-carbon material, and the solid electrolyte can effectively improve the lithium ion conductivity of the silicon-carbon material, so that the impedance and the polarization degree are effectively reduced, and the purpose of improving the electrochemical performance of the lithium battery is realized.
In addition, the battery negative electrode material contains heteroatoms such as N, S, P element due to the carbon-oxide electrolyte, so that the conductivity of the battery negative electrode material can be improved, and an additional chemical site can be provided for lithium ions, thereby improving the lithium storage performance of the lithium battery.
In addition, the preparation method of the invention also has the advantages and beneficial effects.
It should be noted that the prior art in the protection scope of the present invention is not limited to the examples given in the present application, and all the prior art which is not inconsistent with the technical scheme of the present invention, including but not limited to the prior patent documents, the prior publications and the like, can be included in the protection scope of the present invention.
In addition, the combination of the features in the present application is not limited to the combination described in the claims of the present application or the combination described in the embodiments, and all the features described in the present application may be freely combined or combined in any manner unless contradictory to each other.
It should also be noted that the above-mentioned embodiments are only specific examples of the present invention, and it is obvious that the present invention is not limited to the above-mentioned embodiments, and many similar variations are possible. All modifications which would occur to one skilled in the art and which are, therefore, directly derived or suggested from the disclosure herein are deemed to be within the scope of the present invention.

Claims (11)

1. A carbon-oxide electrolyte coated battery negative electrode material, comprising: the battery negative electrode material used as the core part is coated with a carbon-oxide electrolyte layer.
2. The carbon-oxide electrolyte coated battery anode material according to claim 1, wherein the battery anode material comprises: at least one of silicon carbon, graphite, soft carbon, and hard carbon.
3. The carbon-oxide electrolyte coated battery anode material of claim 1, wherein the oxide electrolyte in the carbon-oxide electrolyte layer comprises: li7La3Zr2O12，0.2Al-Li7La3Zr2O12，Ba-Sb-Li7La3Zr2O12，Ge-Li7La3Zr2O12，Li6.75La3Zr1.75Ta0.25O12，Li6.75La3Zr1.75Nb0.25O12At least one of (a).
4. The method of preparing a carbon-oxide electrolyte coated battery anode material according to any one of claims 1 to 3, comprising the steps of:
mixing a battery negative electrode material, a carbon source organic matter and nano-scale oxide electrolyte particles through ball milling; and then high-temperature calcination is carried out to obtain the battery negative electrode material coated with the carbon-oxide electrolyte.
5. The method of claim 4, wherein the carbon source organic material comprises: at least one of polyethylene oxide, polyethylene glycol, sucrose, glucose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, polyacrylate, polyurethane, cellulose, starch, amino acid, melamine, dicyandiamide, phenolic resin and epoxy resin.
6. The production method according to claim 4, wherein the size of the oxide electrolyte particle is 500nm or less.
7. The method of claim 4, wherein the ball milling is performed with process parameters that satisfy at least one of:
the ball milling speed is 100-;
the ball milling time is 1-24 h;
the ball-material ratio is 1-100.
8. The method of claim 4, wherein the calcination temperature is 500-900 ℃.
9. The method of claim 4, wherein the atmosphere for the calcination is at least one of nitrogen, argon, helium, and ammonia.
10. The method of claim 4, wherein the calcining step comprises heating to the calcining temperature at a rate of 0.5-20 ℃/min for a period of 0.5-6 hours.
11. The production method according to claim 4, wherein the battery negative electrode material, the carbon source organic matter and the oxide electrolyte particles are mixed in a mass part ratio of (70-95) to (5-20) to (5-15).
CN201910925563.4A 2019-07-26 2019-09-27 Carbon-oxide electrolyte coated battery negative electrode material and preparation method thereof Pending CN112301271A (en)

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