CN110707310B - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cathode material and a preparation method and application thereof, wherein the cathode material is of a core-shell structure, and the core is LiaSn alloy nanoparticles and SiOxAnd the LiaSn alloy nano particles are compounded on the SiOxWherein a is 0.8. ltoreq. a.ltoreq.4.4, the shell being amorphous carbon. The cathode material has high first efficiency and long cycle life.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative electrode material and a preparation method and application thereof.
Background
Currently, lithium ion batteries have gradually merged into every part of life as mature energy storage units. In the life, electrical appliances such as mobile phones and notebooks use lithium ion batteries as their energy storage units, and in recent years, lithium ion batteries are also gradually used in the field of power energy storage, such as electric vehicles.
For a lithium ion battery, the most influential factors on its energy density should be the positive electrode material and the negative electrode material. The graphite cathode material of the lithium ion battery used in commercialization at present has lower theoretical capacity, and the space for further improving the capacity is very small, so that the graphite cathode material can not meet the requirements of future high-capacity and long-service-life electronic equipment. The metal and alloy materials are novel high-efficiency lithium storage negative electrode materials which are researched more in recent years, wherein the silicon-oxygen material is concerned about due to the fact that the silicon-oxygen material has extremely high theoretical specific capacity, but the silicon-oxygen material can form some irreversible capacity byproducts during first charging, and therefore the first efficiency of the battery is far from reaching the application standard.
In order to overcome the defects, researchers make a lot of attempts to improve the first efficiency of the silicon-oxygen-carbon lithium ion battery by adopting electrochemical pre-lithium, chemical pre-lithium and other methods, but because lithium metal is more active electrochemically and cannot be used in a normal environment, the preparation of a lithium supplement material which stably exists in a normal temperature and humidity environment is urgent. However, the improvement direction aiming at the first lower efficiency of the silicon-oxygen-carbon composite material is only lithium supplement of a negative pole piece, or electrochemical pre-lithium under the condition of higher experimental environment requirements, so that the improvement cannot be completed.
Therefore, the existing anode material is in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a negative electrode material, and a preparation method and application thereof. The cathode material has high first efficiency and long cycle life.
In one aspect of the invention, the invention proposes an anode material which, according to an embodiment of the invention, is of a core-shell structure, the core being LiaSn alloy nanoparticles and SiOxAnd the LiaSn alloy nano particles are compounded on the SiOxWherein a is 0.8. ltoreq. a.ltoreq.4.4, the shell being amorphous carbon.
According to the negative electrode material provided by the embodiment of the invention, the negative electrode material has a core-shell structure, and the shell is amorphous carbon, so that a stable SEI (solid electrolyte interphase) film can be formed on the negative electrode, and the cycle stability of the negative electrode is improved. While the nucleus is LiaSn alloy nanoparticles and SiOxComposite material of (2), SiOxCan be used as an active material to provide lithium storage capacity. Furthermore, Sn and Si can be tightly combined due to the similar chemical properties of the Sn and the Si, so that LiaSn alloy nanoparticles and SiOxThe composite material has stable structure. Further, due to LiaSn alloy nano-particles are compounded in SiOxSurface of (2), LiaThe primary efficiency of the Sn alloy nano particles can reach 237 percent, and the Sn alloy nano particles can stably exist for more than 8 hours in normal temperature and humidity environment, so that LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxFirst effect ofThe rate is improved by 3-5%. Thus, the anode material has high first efficiency and long cycle life.
In addition, the anode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the LiaSn alloy nanoparticles and SiOxThe mass ratio of (A) to (B) is 10: 1.5-3.
In some embodiments of the invention, the LiaThe particle size of the Sn alloy nano-particles is 150-200 nm.
In some embodiments of the invention, the SiOxHas a particle diameter of 5-8 μm.
In some embodiments of the invention, the shell has a thickness of 2-3 μm.
In some embodiments of the invention, the amorphous carbon is selected from at least one of phenolic resin, pitch, sucrose.
In some embodiments of the invention, the mass ratio of the core to the shell is 100: 8-10.
In still another aspect of the present invention, the present invention provides a method of preparing the above negative electrode material, according to an embodiment of the present invention, the method including:
(1) lithium is melt-mixed with tin to obtain bulk LiaSn alloy, ball milling to obtain LiaSn alloy nanoparticles;
(2) subjecting the Li toaSn alloy nanoparticles and SiOxMixing and ball milling reaction protecting solvent to obtain LiaSn·SiOxA composite material;
(3) subjecting the Li toaSn·SiOxAnd mixing the composite material with amorphous carbon and an organic solvent, drying and calcining to obtain the negative electrode material.
According to the method for preparing the anode material of the embodiment of the invention, the lithium and the tin are melted and mixed, so that the massive Li stably existing for more than 8 hours under normal temperature and humidity environment can be preparedaSn alloy, bulk LiaAfter ball milling, the Sn alloy can stably exist for more than 8h in normal temperature and humidity environmentLi of (2)aSn alloy nanoparticles, the LiaThe Sn alloy nano particles have high primary efficiency which can be as high as 237 percent at most; because of the close chemical properties of Sn and Si, the Sn and Si can be tightly combined by combining LiaSn alloy nanoparticles and SiOxThe mixed ball milling of the reaction protective solvent can avoid Li under the protection of the reaction protective solventaSn alloy nanoparticles and/or SiOxCan be changed, and further can avoid affecting LiaSn·SiOxQuality of the composite material. Further, after mixing and ball milling, LiaSn alloy nano-particles can be stably compounded in SiOxSurface of Li in the structureaSn·SiOxIn the composite material, SiOxAs active material, providing lithium storage capacity, LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxThe first efficiency is improved by 3-5%; further, by adding LiaSn·SiOxThe composite material is mixed with the amorphous carbon and the organic solvent, and the organic solvent is favorable for promoting the dispersion of the amorphous carbon, so that the amorphous carbon is uniformly coated on LiaSn·SiOxAfter drying and calcining the surface of the composite material, volatilizing the organic solvent to obtain the cathode material with a core-shell structure, wherein the amorphous shape of the shell layer is beneficial to the cathode to form a stable SEI film, and the cycle stability of the cathode is improved. Therefore, the method can be used for preparing the core-shell structure cathode material with high first efficiency and long cycle life.
In addition, the method for preparing the anode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the calcining in step (1), step (2) and step (3) is performed under an inert atmosphere.
In some embodiments of the invention, in step (1) and step (2), the pressure of the inert atmosphere is independently 0.1 to 0.3 MPa.
In some embodiments of the present invention, in step (1), the ball milling speed is 300-500rpm for 35-45 h.
In some embodiments of the invention, in step (2), the reaction protection solvent is selected from at least one of dodecene, tetradecene, hexadecene, octadecene.
In some embodiments of the invention, in step (2), the ball milling speed is 50-70rpm for 5-15 h.
In some embodiments of the present invention, in step (3), the temperature of the calcination is 600-1000 ℃ and the time is 10-30 h.
In some embodiments of the invention, in step (3), the temperature ramp rate of the calcination is from 1 to 10 ℃/min.
In some embodiments of the invention, in step (3), the organic solvent is selected from anhydrous alcohols.
In some embodiments of the present invention, in step (3), the solid-to-liquid ratio of the amorphous carbon to the organic solvent is 0.1-0.5 g: 20 ml.
In some embodiments of the present invention, in the step (3), the mixed solution of the amorphous carbon and the organic solvent and the LiaSn·SiOxThe liquid-solid ratio of the composite material is 20-30 ml: 1g of the total weight of the composition.
In yet another aspect of the present invention, the present invention provides a lithium ion battery, which includes the above-mentioned negative electrode material or the negative electrode material prepared by the above-mentioned method for preparing the negative electrode material according to an embodiment of the present invention. According to the lithium ion battery provided by the embodiment of the invention, the lithium ion battery contains the core-shell structure cathode material, and the cathode material has high initial efficiency and long cycle life, so that the initial efficiency and the cycle life of the battery are favorably improved, and the performance of the lithium ion battery is further improved.
In yet another aspect of the invention, a vehicle is provided that contains the above-described lithium ion battery according to an embodiment of the invention. According to the vehicle provided by the embodiment of the invention, the vehicle contains the lithium ion battery with high primary efficiency and long cycle life, so that the improvement of the power energy storage capacity of the vehicle is facilitated.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic view of a core-shell structure of an anode material according to an embodiment of the present invention;
fig. 2 is a schematic flow diagram of a method of preparing an anode material according to an embodiment of the invention;
FIG. 3 is as-cast Li1.5Sn alloy and Li obtained in example 11.5An XRD contrast spectrum of the Sn alloy;
FIG. 4 is a graph showing the relationship between the capacity retention rate and the cycle number of batteries manufactured using the anode materials obtained in examples 1 to 3 and comparative example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the present invention, the present invention provides an anode material which has a core-shell structure and a core of Li according to an embodiment of the present invention, referring to fig. 1aSn alloy nanoparticles and SiOxComposite material of, LiaSn alloy nano-particles are compounded in SiOxWherein 0.8. ltoreq. a.ltoreq.4.4, for example a can be 0.8, 1.2, 1.6, 2.0, 2.4, 2.8, 3.2, 3.6, 4.0, 4.4, the shell being amorphous carbon. The inventor finds that the anode material has a core-shell structure, and the shell is amorphous carbon, so that the anode material is beneficial to forming a stable SEI film and improving the cycle stability of the anode. While the nucleus is LiaSn alloy nanoparticles and SiOxComposite material of (2), SiOxCan be used as an active material to provide lithium storage capacity. Further, the reaction of Sn and SiThe two have close chemical properties and can be tightly combined, so that Li is ensuredaSn alloy nanoparticles and SiOxThe composite material has stable structure. Further, due to LiaSn alloy nano-particles are compounded in SiOxSurface of (2), LiaThe primary efficiency of the Sn alloy nano particles can reach 237 percent, and the Sn alloy nano particles can stably exist for more than 8 hours in normal temperature and humidity environment, so that LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxThe first efficiency is improved by 3-5%.
According to one embodiment of the invention, LiaSn alloy nanoparticles and SiOxThe mass ratio of (b) is not particularly limited, and may be selected by those skilled in the art according to actual needs, and may be, for example, 10: 1.5-3, such as 10: 1.5/1.7/2.0/2.2/2.4/2.6/2.8/3. The inventors found that LiaToo low content of Sn alloy nanoparticles to SiOxFirst effect promotion has no obvious effect, LiaThe specific content of the Sn alloy nano particles can be determined according to the SiO required by the actual needsxThe size of the first effect is determined. Further, the mass ratio of the core to the shell is not particularly limited, and can be selected by those skilled in the art according to actual needs, and may be, for example, 100: 8-10, for example 100: 8/8.2/8.5/8.7/9.0/9.3/9.6/9.8/10. The inventor finds that the mass ratio of the core to the shell determines the thickness of the shell, and the excessive thickness of the shell in the material easily causes the particle size of the whole material to be too large, thereby having influence on later-stage homogenization; too thin a shell of SiOxThe shell is easily cracked by volume expansion during cycling.
According to yet another embodiment of the present invention, LiaSn alloy nanoparticles and SiOxThe particle diameter of (A) is not particularly limited and can be selected by those skilled in the art according to practical needs, for example, LiaThe particle size of the Sn alloy nanoparticles can be 150-200nm, such as 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, SiOxThe particle diameter of (B) may be 5 to 8 μm, for example, 5 μm, 6 μm, 7 μm or 8 μm. Therefore, the particle size of the negative electrode material meets the requirement D10 of the current industry on the particle size of the negative electrode material of the lithium ion battery, namely 5-8 μm.
According to yet another embodiment of the present invention, the thickness of the shell is not particularly limited, and may be selected by those skilled in the art according to actual needs, and may be, for example, 2 to 3 μm, such as 2 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm, 3.0 μm. The inventor finds that too thick shell tends to result in too large a particle size of the bulk material, which has an effect on the later homogenization, too thin shell, SiOxThe shell is easily cracked by volume expansion during cycling.
According to yet another embodiment of the invention, SiOxIs not particularly limited, and SiOxNot specifically referring to a particular silicon oxide, e.g. silicon dioxide, SiOxMay be a mixture of a plurality of silicon oxides. In this case, the specific value of x is also not particularly limited, and may be, for example, 0.3 to 1.6. Further, the specific type of amorphous carbon is not particularly limited, and may be any carbon material as long as it has a low degree of graphitization crystallization, a nearly amorphous form, or a structural rule having no fixed shape or periodicity, and may be specifically selected from at least one of phenol resin, pitch, and sucrose, for example. The inventor finds that phenolic resin, asphalt and cane sugar are all organic substances with rich carbon content, and the amorphous carbon can be generated by calcining the organic substances in an inert atmosphere at a certain temperature, so that the residual carbon content of the formed amorphous carbon is different due to different temperatures, and the density of a carbon layer can also have certain influence on the formation of the amorphous carbon.
According to the negative electrode material provided by the embodiment of the invention, the negative electrode material has a core-shell structure, and the shell is amorphous carbon, so that a stable SEI (solid electrolyte interphase) film can be formed on the negative electrode, and the cycle stability of the negative electrode is improved. While the nucleus is LiaSn alloy nanoparticles and SiOxComposite material of (2), SiOxCan be used as an active material to provide lithium storage capacity. Furthermore, Sn and Si can be tightly combined due to the similar chemical properties of the Sn and the Si, so that LiaSn alloy nanoparticles and SiOxThe composite material has stable structure. Further, due to LiaSn alloy nano-particles are compounded in SiOxSurface of (2), LiaThe primary efficiency of the Sn alloy nano particles can reach 237 percent, and the Sn alloy nano particles can stably exist for 8 hours in a normal temperature and humidity environmentAbove, so that LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxThe first efficiency is improved by 3-5%. Thus, the anode material has high first efficiency and long cycle life.
In still another aspect of the present invention, the present invention provides a method of preparing the above-described anode material, according to an embodiment of the present invention, with reference to fig. 2, the method including:
s100: melting and mixing lithium and tin, and ball-milling
In this step, lithium is melt-mixed with tin to obtain bulk LiaSn alloy, ball milling to obtain LiaSn alloy nanoparticles. The inventors found that bulk Li stably existing for 8 hours or more under normal temperature and humidity environment can be obtained by melt-mixing lithium and tinaSn alloy, bulk LiaAfter ball milling of Sn alloy, Li stably existing for more than 8h in normal temperature and humidity environment can be obtainedaSn alloy nanoparticles, the LiaThe Sn alloy nanoparticles have high primary efficiency which can be as high as 237 percent. Specifically, lithium may be melt-mixed with tin under an inert atmosphere, while bulk Li may be melt-mixed under an inert atmosphereaAnd carrying out ball milling on the Sn alloy. Further, tin foil and lithium metal may be treated in an argon atmosphere such as pure argon atmosphere in accordance with LiaPutting the mass ratio of Sn into an induction melting device, setting the working voltage of the induction melting device to be 360V/10A, and obtaining blocky Li after melting and mixingaSn alloy, followed by preparation of the resulting bulk LiaThe Sn alloy is sent to a planetary ball mill in an argon atmosphere such as a pure argon atmosphere for ball milling to obtain Li with the particle size of 150-200nmaSn alloy nano particles, wherein a is more than or equal to 0.8 and less than or equal to 4.4. Further, the pressure of the inert atmosphere during the melting and ball-milling processes may be 0.1 to 0.3MPa, such as 0.1MPa, 0.14MPa, 0.17MPa, 0.2MPa, 0.23MPa, 0.26MPa, and 0.3MPa, respectively. The inventor finds that the pressure of the inert atmosphere is too low, air can exist in the ball milling and melting process, the material has oxidation risk, the requirement on equipment is higher due to the too high pressure of the inert atmosphere, and equipment is addedAnd (4) cost. Further, the conditions of the ball milling are not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the ball milling speed can be 300-500rpm, such as 300rpm, 330rpm, 360rpm, 400rpm, 440rpm, 480rpm, 500rpm, and the time can be 35-45h, such as 35h, 37h, 39h, 41h, 43h, 45 h. Further, the purity of lithium and tin metal is not particularly limited, and those skilled in the art can select the purity according to actual needs, for example, the purity of tin may be not less than 99.5%, and the purity of lithium may be not less than 99.9%. Thereby, Li is advantageously increasedaQuality of Sn alloy nanoparticles.
S200: mixing LiaSn alloy nanoparticles and SiOxAnd ball milling with mixed reaction protecting solvent
In this step, Li is addedaSn alloy nanoparticles and SiOxMixing and ball milling reaction protecting solvent to obtain LiaSn·SiOxA composite material. The inventors have found that Sn and Si can be tightly bonded by combining Li with them due to their close chemical propertiesaSn alloy nanoparticles and SiOxThe mixed ball milling of the reaction protective solvent can avoid Li under the protection of the reaction protective solventaSn alloy nanoparticles and/or SiOxCan be changed, and further can avoid affecting LiaSn·SiOxQuality of the composite material. Further, Li with small particle size after mixed ball millingaThe Sn alloy nano-particles can be stably compounded in SiO with relatively large particle sizexSurface of Li in the structureaSn·SiOxIn the composite material, SiOxAs active material, providing lithium storage capacity, LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxThe first efficiency is improved by 3-5%. Specifically, Li may be added under an inert atmosphereaSn alloy nanoparticles and SiOxThe reaction protecting solvent is mixed and ball milled, for example, in argon atmosphere, and further, in pure argon atmosphere. Further, Li having a particle size of 150-200nm may be usedaSn alloy nano-particles and SiO with particle size of 5-8 mu mxAccording to massAnd (2) the ratio of 10: 1.5-3, sending into a planetary ball mill, adding a small amount of reaction protective solvent to carry out mixed ball milling under the atmosphere of pure argon gas so as to obtain LiaSn·SiOxA composite material. The pressure of the inert atmosphere during the ball milling is not particularly limited, and may be selected by those skilled in the art according to the actual need, and may be, for example, 0.1 to 0.3MPa, such as 0.1MPa, 0.14MPa, 0.17MPa, 0.2MPa, 0.23MPa, 0.26MPa, or 0.3 MPa. The inventor finds that the pressure of the inert atmosphere is too low, air can exist in the ball milling and melting process, the material has oxidation danger, and the requirement on equipment is high due to the too high pressure of the inert atmosphere, so that the equipment cost is increased. Further, the specific type of the reaction-protecting solvent is not particularly limited, and may be selected by those skilled in the art according to the actual need, as long as Li is compatible therewithaSn alloy nanoparticles and SiOxThe protective effect may be, for example, at least one selected from the group consisting of dodecene, tetradecene, hexadecene, and octadecene. Further, the amount of the reaction protecting solvent to be added is not particularly limited, and may be selected by those skilled in the art according to the actual need. The conditions of the ball milling are not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the ball milling speed can be 50-70rpm, such as 50rpm, 53rpm, 56rpm, 60rpm, 64rpm, 68rpm, 70rpm, and the time can be 5-15h, such as 5h, 7h, 9h, 11h, 13h, 15 h.
S300: mixing LiaSn·SiOxMixing the composite material with amorphous carbon and organic solvent, drying and calcining
In this step, Li is addedaSn·SiOxAnd mixing the composite material with amorphous carbon and an organic solvent, drying and calcining to obtain the negative electrode material. The inventors have found that by incorporating LiaSn·SiOxThe composite material is mixed with the amorphous carbon and the organic solvent, and the organic solvent is favorable for promoting the dispersion of the amorphous carbon, so that the amorphous carbon is uniformly coated on LiaSn·SiOxDrying and calcining the surface of the composite material, and volatilizing the organic solvent to obtain the cathode material with a core-shell structure, wherein the amorphous shape of the shell layer is favorable for forming a more stable cathodeAnd the determined SEI film improves the cycle stability of the negative electrode. Specifically, the amorphous carbon and the organic solvent may be mixed to uniformly disperse the amorphous carbon in the organic solvent to obtain a mixed solution, and then Li obtained in S200 may be addedaSn·SiOxAnd adding the composite material into the mixed solution, uniformly mixing, performing spray drying, and calcining in an inert atmosphere to obtain the cathode material. Wherein LiaSn·SiOxThe mass ratio of the composite material to the amorphous carbon is 100: 8-10. Further, the specific type of the organic solvent is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, it can be anhydrous alcohols, such as anhydrous ethanol, etc. Further, the solid-to-liquid ratio of the amorphous carbon to the organic solvent is not particularly limited, and may be selected by those skilled in the art according to actual needs, and may be, for example, 0.1 to 0.5 g: 20ml, such as may be 0.1/0.2/0.3/0.4/0.5 g: 20 ml. The inventor finds that the liquid proportion is too low, so that the solid content of the mixed liquid is too high to be adjusted to LiaSn·SiOxAnd dispersing and coating the composite material. Further, a mixed solution of amorphous carbon and an organic solvent and LiaSn·SiOxThe liquid-solid ratio of the composite material is not particularly limited, and can be selected by those skilled in the art according to actual needs, and can be, for example, 20 to 30 ml: 1g, such as can be 20/22/24/26/28/30 ml: 1g of the total weight of the composition. The inventors have found that a mixed solution containing amorphous carbon and LiaSn·SiOxThe liquid-to-solid ratio of the composite material determines the relative thickness of the shell. Too thick shell tends to result in too large particle size of the bulk material, which affects later homogenization, too thin shell, SiOxThe shell is easily cracked by volume expansion during cycling. Further, the calcination conditions are not particularly limited, and those skilled in the art can select them according to the actual needs, for example, the calcination temperature can be 600-1000 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, and the time can be 10-30h, such as 10h, 13h, 16h, 20h, 24h, 27h, and 30 h. Further, the temperature rising rate during the calcination process is not particularly limited, and can be selected by those skilled in the art according to the actual requirement, for example, it can be 1-10 deg.C/min, such as 1/2/4/6/8%10 ℃/min. The inventors found that the rate of temperature increase during calcination has an effect on the volatilization of the volatile components of the organic carbon source.
It should be noted that the characteristics and advantages of the above-mentioned negative electrode material are also applicable to the method for preparing the negative electrode material, and are not described again.
According to the method for preparing the anode material of the embodiment of the invention, the lithium and the tin are melted and mixed, so that the massive Li stably existing for more than 8 hours under normal temperature and humidity environment can be preparedaSn alloy, bulk LiaAfter ball milling of Sn alloy, Li stably existing for more than 8h in normal temperature and humidity environment can be obtainedaSn alloy nanoparticles, the LiaThe Sn alloy nano particles have high primary efficiency which can be as high as 237 percent at most; because of the close chemical properties of Sn and Si, the Sn and Si can be tightly combined by combining LiaSn alloy nanoparticles and SiOxThe mixed ball milling of the reaction protective solvent can avoid Li under the protection of the reaction protective solventaSn alloy nanoparticles and/or SiOxCan be changed, and further can avoid affecting LiaSn·SiOxQuality of the composite material. Further, after mixing and ball milling, LiaSn alloy nano-particles can be stably compounded in SiOxSurface of Li in the structureaSn·SiOxIn the composite material, SiOxAs active material, providing lithium storage capacity, LiaThe Sn alloy nanoparticles can provide a certain lithium source to improve SiOxFirst efficiency of the material, SiOxThe first efficiency is improved by 3-5%; further, by adding LiaSn·SiOxThe composite material is mixed with the amorphous carbon and the organic solvent, and the organic solvent is favorable for promoting the dispersion of the amorphous carbon, so that the amorphous carbon is uniformly coated on LiaSn·SiOxAfter drying and calcining the surface of the composite material, volatilizing the organic solvent to obtain the cathode material with a core-shell structure, wherein the amorphous shape of the shell layer is beneficial to the cathode to form a stable SEI film, and the cycle stability of the cathode is improved. Therefore, the method can be used for preparing the core-shell structure cathode material with high first efficiency and long cycle life.
In yet another aspect of the present invention, the present invention provides a lithium ion battery, which includes the above-mentioned negative electrode material or the negative electrode material prepared by the above-mentioned method for preparing the negative electrode material according to an embodiment of the present invention. According to the lithium ion battery provided by the embodiment of the invention, the lithium ion battery contains the core-shell structure cathode material, and the cathode material has high initial efficiency and long cycle life, so that the initial efficiency and the cycle life of the battery are favorably improved, and the performance of the lithium ion battery is further improved. It should be noted that the characteristics and advantages of the negative electrode material or the method for preparing the negative electrode material are also applicable to the lithium ion battery, and are not described again.
In yet another aspect of the invention, a vehicle is provided that contains the above-described lithium ion battery according to an embodiment of the invention. According to the vehicle provided by the embodiment of the invention, the vehicle contains the lithium ion battery with high primary efficiency and long cycle life, so that the improvement of the power energy storage capacity of the vehicle is facilitated. It should be noted that the characteristics and advantages of the lithium ion battery are also applicable to the vehicle, and are not described again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
EXAMPLE 1
(1) Sn foil with the purity of 99.5% and Li foil with the purity of 99.9% are mixed according to the molar ratio of 1: 1.5 feeding the mixture into an induction smelting device in a pure argon atmosphere, wherein the working voltage of the induction smelting device is 360V, the working current of the induction smelting device is 10A, and after the mixture is melted and mixed, blocky Li is obtained1.5Sn alloy, followed by the addition of the bulk Li1.5Transferring the Sn alloy into a planetary ball mill with a pure argon atmosphere of 0.1-0.3MPa for ball milling at the ball milling speed of 300rpm for 40h to obtain Li with the particle size of about 150nm1.5The XRD pattern of Sn alloy nanoparticles is shown in FIG. 3, and it can be seen from FIG. 3 that Li prepared by the method described above1.5XRD (X-ray diffraction) pattern of Sn alloy nano particles and Li of as-cast structure1.5Uniformity of Sn alloys, i.e. Li can be prepared by the above method1.5Sn alloy;
(2) the Li obtained in the step (1) is1.5The mass ratio of the Sn alloy nano particles to SiO with the particle size of 5-8 mu m is 10: 3, sending the mixture into a planetary ball mill in a pure argon atmosphere of 0.1-0.3MPa, simultaneously adding a small amount of hexadecene for wetting, and carrying out ball milling for 10 hours at the rotating speed of 50rpm to obtain Li1.5A Sn SiO composite material;
(3) mixing phenolic resin with absolute ethyl alcohol according to the weight ratio of 0.1 g: mixing the materials at a solid-to-liquid ratio of 20ml to uniformly disperse the phenolic resin in absolute ethyl alcohol to obtain a mixed solution, and then adding the Li obtained in the step (2)1.5Adding the Sn-SiO composite material into the mixed solution, dispersing and stirring for 4h, wherein Li1.5The solid-to-liquid ratio of the Sn-SiO composite material to the mixed solution is 1 g: 20ml of uniformly stirred liquid is dried in a spray dryer at the flow rate of 15ml/min, the dried substance is collected and sent to a box furnace, the temperature is increased to 900 ℃ at the speed of 3 ℃/min under the Ar atmosphere, then the calcined substance is calcined for 24h, and the calcined substance is taken out and sieved to obtain the cathode material.
EXAMPLE 2
(1) Sn foil with the purity of 99.5% and Li foil with the purity of 99.9% are mixed according to the molar ratio of 1: 3, feeding the mixture into an induction smelting device in a pure argon atmosphere, wherein the working voltage of the induction smelting device is 360V, the working current of the induction smelting device is 10A, and obtaining blocky Li after the materials are melted and mixed3Sn alloy, followed by the addition of the bulk Li3Transferring the Sn alloy into a planetary ball mill with a pure argon atmosphere of 0.1-0.3MPa for ball milling at a ball milling speed of 300rpm for 40h to obtain Li with a particle size of about 180nm3Sn alloy nanoparticles;
(2) the Li obtained in the step (1) is3The mass ratio of the Sn alloy nano particles to SiO with the particle size of 5-8 mu m is 10: 2, sending the mixture into a planetary ball mill in a pure argon atmosphere of 0.1-0.3MPa, simultaneously adding a small amount of hexadecene for wetting, and carrying out ball milling for 10 hours at the rotating speed of 50rpm to obtain Li3Sn·SiO0.3A composite material;
(3) mixing phenolic resin with absolute ethyl alcohol according to the weight ratio of 0.3 g: mixing the materials at a solid-to-liquid ratio of 20ml to uniformly disperse the phenolic resin in absolute ethyl alcohol to obtain a mixed solution, and then adding the Li obtained in the step (2)3Sn·SiO0.3Adding the composite material into the mixed solutionStirring for 4h, wherein Li3Sn·SiO0.3The solid-liquid ratio of the composite material to the mixed liquid is 1 g: 25ml of uniformly stirred liquid is dried in a spray dryer at the flow rate of 15ml/min, the dried substance is collected and sent to a box furnace, the temperature is increased to 900 ℃ at the speed of 3 ℃/min under the Ar atmosphere, then the calcined substance is calcined for 24h, and the calcined substance is taken out and sieved to obtain the cathode material.
EXAMPLE 3
(1) Sn foil with the purity of 99.5% and Li foil with the purity of 99.9% are mixed according to the molar ratio of 1: 4.4 feeding the mixture into an induction smelting device in a pure argon atmosphere, wherein the working voltage of the induction smelting device is 360V, the working current of the induction smelting device is 10A, and obtaining blocky Li after the materials are melted and mixed4.4Sn alloy, followed by the addition of the bulk Li4.4Transferring the Sn alloy into a planetary ball mill with a pure argon atmosphere of 0.1-0.3MPa for ball milling at a ball milling speed of 300rpm for 40h to obtain Li with a particle size of about 200nm4.4Sn alloy nanoparticles;
(2) the Li obtained in the step (1) is4.4The mass ratio of the Sn alloy nano particles to SiO with the particle size of 5-8 mu m is 10: 1.5 sending into a planetary ball mill with pure argon atmosphere of 0.1-0.3MPa, simultaneously adding a small amount of hexadecene for wetting, and ball-milling at the rotating speed of 50rpm for 10h to obtain Li4.4Sn·SiO1.6A composite material;
(3) mixing phenolic resin with absolute ethyl alcohol according to the weight ratio of 0.5 g: mixing the materials at a solid-to-liquid ratio of 20ml to uniformly disperse the phenolic resin in absolute ethyl alcohol to obtain a mixed solution, and then adding the Li obtained in the step (2)4.4Sn·SiO1.6Adding the composite material into the mixed solution, dispersing and stirring for 4h, wherein Li4.4Sn·SiO1.6The solid-liquid ratio of the composite material to the mixed liquid is 1 g: 30ml of uniformly stirred liquid is dried in a spray dryer at the flow rate of 15ml/min, the dried substance is collected and sent to a box furnace, the temperature is increased to 900 ℃ at the speed of 3 ℃/min under the Ar atmosphere, then the calcined substance is calcined for 24h, and the calcined substance is taken out and sieved to obtain the cathode material.
Comparative example 1
Mixing phenolic resin with absolute ethyl alcohol according to the weight ratio of 0.1 g: mixing at a solid-to-liquid ratio of 20ml to uniformly disperse the phenolic resin in absolute ethyl alcohol to obtain a mixed solution, adding SiO with a particle size of 5-8 mu m into the mixed solution, and stirring for 4 hours, wherein the solid-to-liquid ratio of SiO to the mixed solution is 1 g: 20ml of uniformly stirred liquid is dried in a spray dryer at the flow rate of 15ml/min, the dried substance is collected and sent to a box furnace, the temperature is increased to 900 ℃ at the speed of 3 ℃/min under the Ar atmosphere, then the calcined substance is calcined for 24h, and the calcined substance is taken out and sieved to obtain the cathode material.
The negative electrode materials obtained in examples 1 to 3 and comparative example 1 were respectively prepared into button cells and tested, wherein the type of the button cells is CR2430, and LiPF is contained in electrolyte6: EC: DEC: PP 1: 1.78: 3.57: 1.4; the negative electrode comprises 3.0 wt% of PAA, 1.0 wt% of SP, 3.0 wt% of CMC and the balance of the negative electrode material; the counter electrode is a pure lithium sheet. The charge and discharge performance of the obtained negative electrode materials are shown in table 1, and the cycle curve is shown in fig. 4.
TABLE 1 Charge/discharge Properties of coin cells prepared using the negative electrode materials obtained in examples 1 to 3 and comparative example 1
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (17)
1. The negative electrode material is characterized in that the negative electrode material is of a core-shell structure, and the core is LiaSn alloy nanoparticles and SiOxX is 0.3 to 1.6, and the LiaSn alloy nano particles are compounded on the SiOxWherein a is not less than 0.8 and not more than 4.4, and the shell is amorphous carbon;
the LiaSn alloy nanoparticles and SiOxThe mass ratio of (A) to (B) is 10: 1.5-3;
the LiaThe particle size of the Sn alloy nano particles is 150-200 nm;
the SiOxHas a particle diameter of 5-8 μm.
2. The anode material according to claim 1, wherein the shell has a thickness of 2 to 3 μm.
3. The anode material of claim 1, wherein the amorphous carbon is selected from at least one of phenolic resin, pitch, sucrose.
4. The anode material according to claim 1, wherein a mass ratio of the core to the shell is 100: 8-10.
5. A method of preparing the anode material of any one of claims 1 to 4, comprising:
(1) lithium is melt-mixed with tin to obtain bulk LiaSn alloy, ball milling to obtain LiaSn alloy nanoparticles;
(2) subjecting the Li toaSn alloy nanoparticles and SiOxMixing and ball milling reaction protecting solvent to obtain LiaSn·SiOxA composite material;
(3) subjecting the Li toaSn·SiOxComposite materialMixing with amorphous carbon and organic solvent, drying and calcining to obtain the cathode material.
6. The method of claim 5, wherein the melting in step (1), the ball milling in step (2), and the calcining in step (3) are performed under an inert atmosphere.
7. The method of claim 6, wherein the pressure of the inert atmosphere in step (1) and step (2) is independently 0.1 to 0.3 MPa.
8. The method as claimed in claim 5, wherein in step (1), the ball milling speed is 300-500rpm for 35-45 h.
9. The method of claim 5, wherein in step (2), the reaction protection solvent is selected from at least one of dodecalene, tetradecene, hexadecene, octadecene.
10. The method of claim 5, wherein in step (2), the ball milling speed is 50-70rpm and the time is 5-15 h.
11. The method as claimed in claim 5, wherein in step (3), the calcination temperature is 600-1000 ℃ and the calcination time is 10-30 h.
12. The method according to claim 5, wherein in step (3), the temperature increase rate of the calcination is 1-10 ℃/min.
13. The method according to claim 5, wherein in step (3), the organic solvent is selected from anhydrous alcohols.
14. The method according to claim 5, wherein in step (3), the solid-to-liquid ratio of the amorphous carbon to the organic solvent is 0.1-0.5 g: 20 ml.
15. The method according to claim 5, wherein in step (3), the mixed solution of the amorphous carbon and the organic solvent and the LiaSn·SiOxThe liquid-solid ratio of the composite material is 20-30 ml: 1g of the total weight of the composition.
16. A lithium ion battery having the negative electrode material of any one of claims 1 to 4 or the negative electrode material prepared by the method of any one of claims 5 to 15.
17. An automobile comprising the lithium ion battery of claim 16.
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