CN111834613B - High-capacity composite negative electrode material, preparation method and lithium ion battery - Google Patents
High-capacity composite negative electrode material, preparation method and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a high-capacity composite negative electrode material, a preparation method thereof and a lithium ion battery, and relates to the field of lithium ion batteries. The composite cathode material provided by the invention takes the hard carbon as a framework, takes the cobalt tetraoxide ferrate nanowire bonded with the hard carbon as a high-capacity provider, and further coats a carbon coating layer on the outer parts of the hard carbon and the cobalt tetraoxide ferrate nanowire, so that the composite cathode material provided by the invention has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of a lithium ion battery on the composite cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-capacity composite negative electrode material, a preparation method thereof and a lithium ion battery.
Background
With the advancement of science and technology, consumers have higher requirements on the performance of electric vehicles and electronic products, and at the same time, the requirements on the performance of lithium ion batteries as power providers of electric vehicles and electronic products have also been higher.
The cathode material is used as one of the core components of the lithium ion battery, and plays a key role in improving the comprehensive performance of the lithium ion battery. The conventional negative electrode material of the lithium ion battery has the problems of difficult capacity improvement and low capacity of the negative electrode material.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a high-capacity composite negative electrode material, wherein the high-capacity composite negative electrode material comprises hard carbon, a cobalt tetraoxide ferrite nanowire and a carbon coating layer, wherein the hard carbon is a framework of the high-capacity composite negative electrode material, the cobalt tetraoxide ferrite nanowire is bonded with the hard carbon, and the carbon coating layer is coated outside the hard carbon and the cobalt tetraoxide ferrite nanowire.
Another object of the present invention is to provide a method for preparing a high-capacity composite anode material, which is used for preparing the high-capacity composite anode material, and comprises:
s1: mixing citric acid and ethylene glycol to obtain a solution A;
s2: weighing iron salt and cobalt salt, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat to obtain sol C;
s4: adding an alumina molecular sieve into the sol C, stirring at the temperature of 80-120 ℃, and filtering to obtain particles D;
s5: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat to obtain particles E;
s6: impregnating the particles E with an alkali solution, separating insoluble substances, and washing the insoluble substances to be neutral to obtain cobalt tetraoxydiphosphate nanowires;
s7: mixing hard carbon with the cobalt tetraoxydiphosphate nanowire to obtain powder F;
s8: and (3) introducing organic gas into the powder F at the temperature of 800-1200 ℃ to perform chemical vapor deposition to obtain the high-capacity composite anode material.
Optionally, the mass ratio of the citric acid to the ethylene glycol ranges from 1:8 to 1: 4.
Optionally, the iron salt comprises at least one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferric acetate, ferric citrate, ferrocene, ferrous oxalate, ferric phosphate; the cobalt salt comprises at least one of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate and cobalt acetate; the molar ratio of the iron element to the cobalt element in the raw material B is 2: 1-2: 1.2.
Optionally, the step of adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat to obtain the sol C comprises: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat for 1-5 hours to obtain sol C; the mass of the solution A is 10-50 times of that of the raw material B.
Optionally, the adding an alumina molecular sieve into the sol C, stirring at a temperature of 80-120 ℃, and filtering to obtain particles D includes: adding the alumina molecular sieve into the sol C, stirring for 1-10 hours at the temperature of 80-120 ℃, and filtering to obtain particles D; wherein the mass of the sol C is 2-10 times of that of the alumina molecular sieve.
Optionally, heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat to obtain particles E includes: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat for 1-5 hours to obtain particles E; wherein the oxidizing atmosphere comprises at least one of an oxygen atmosphere and an air atmosphere.
Optionally, the mass ratio of the hard carbon to the cobalt tetraoxide ferrate nanowires ranges from 2:1 to 10: 1; the particle size range of the hard carbon is 5-30 microns.
Optionally, introducing an organic gas into the powder F at a temperature of 800-1200 ℃ to perform chemical vapor deposition, so as to obtain a high-capacity composite anode material, wherein the high-capacity composite anode material comprises: introducing organic gas into the powder F at the temperature of 800-1200 ℃, and performing chemical vapor deposition for 5-60 minutes to obtain a high-capacity composite negative electrode material; wherein the organic gas comprises at least one of methane, ethane, acetylene, acetone, benzene, toluene, and xylene.
Still another object of the present invention is to provide a lithium ion battery comprising the above-mentioned high capacity type composite anode material.
Compared with the prior art, the invention has the beneficial effects that:
the composite negative electrode material provided by the invention takes hard carbon as a framework, takes cobalt tetraoxide ferrate nanowires bonded with the hard carbon as a high-capacity provider, and further coats a carbon coating layer on the outer parts of the hard carbon and the cobalt tetraoxide ferrate nanowires, so that the composite negative electrode material provided by the invention has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of a lithium ion battery on the composite negative electrode material;
2, the preparation method of the high-capacity composite negative electrode material provided by the invention is characterized in that iron salt and cobalt salt are used as raw materials, an alumina molecular sieve is used as a template method to prepare the cobalt tetraoxide ferrate nanowire, then hard carbon is mixed with the cobalt tetraoxide ferrate nanowire, and a carbon coating layer is prepared outside the hard carbon and the cobalt tetraoxide ferrate nanowire, so that the preparation method is simple and the cost is low; the prepared composite negative electrode material has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of the lithium ion battery on the composite negative electrode material.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a scanning electron microscope image of a high capacity type composite anode material of the present invention;
FIG. 2 is a graph of the 1C cycle life of the high capacity type composite anode material of the present invention;
fig. 3 is a schematic flow chart of a method for preparing a high-capacity composite anode material according to the present invention.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
At present, the negative electrode material of the lithium ion battery is mainly the traditional graphite negative electrode material, and the capacity of the commercially available graphite negative electrode material is close to the theoretical capacity of the graphite negative electrode material, so that the problem that the capacity of the graphite negative electrode material is difficult to improve exists; in order to enable the capacity of the cathode material to meet the requirement of a lithium ion battery, the invention provides a high-capacity type composite cathode material which comprises hard carbon, a cobalt tetraoxide ferrite nanowire and a carbon coating layer, wherein the hard carbon is a framework of the high-capacity type composite cathode material, the cobalt tetraoxide ferrite nanowire is bonded with the hard carbon, and the carbon coating layer is coated outside the hard carbon and the cobalt tetraoxide ferrite nanowire.
In the composite negative electrode material provided by the invention, cobalt tetraoxydi-ferrate (CoFe)2O4) can reach 3 times of the theoretical capacity of graphite, and the capacity of the composite cathode material is greatly improved by introducing cobalt tetraoxide ferrate into the composite cathode material as a high-capacity provider of the cathode material; the cobalt tetraoxide ferrate is further introduced in a form of a nanowire, namely the cobalt tetraoxide ferrate nanowire is bonded with hard carbon, adverse effects caused by volume expansion in the charge-discharge process of the cobalt tetraoxide ferrate are reduced by nanocrystallizing the cobalt tetraoxide ferrate, the migration path of lithium ions is shortened, and the comprehensive performance of the composite cathode material is improved.
The interlayer spacing of the hard carbon material is larger than the radius of lithium ions, so when the hard carbon material is used as a negative electrode material of a lithium ion battery, the volume of the hard carbon material is not changed in the charge and discharge processes of the lithium ion battery, cobalt tetraoxide ferrate has the characteristics of high specific capacity, large charge and discharge volume expansion and contraction amplitude and low conductivity, the hard carbon is used as a main material of the composite negative electrode material by bonding the cobalt tetraoxide ferrate nanowires and the hard carbon as a framework, and the expansion and contraction rate of the hard carbon material plays a decisive role in the expansion and contraction rate and the conductivity of the composite negative electrode material in the charge and discharge processes, so that the composite negative electrode material provided by the invention has high specific capacity, high specific capacity and low conductivity simultaneously by taking the hard carbon material as the main material and the cobalt tetraoxide ferrate as a capacity provider in a synergistic effect of the hard carbon material and the hard carbon material, Long cycle life and good rate capability.
In order to further increase the stability of the performance of the composite cathode material, a carbon coating layer is coated outside the hard carbon and the cobalt tetraoxide ferrate, so that on one hand, the connection strength between the hard carbon and the cobalt tetraoxide ferrate is increased, the processability of the composite cathode material is improved, the stability and the consistency of the performance of the composite cathode material are improved, the hard carbon and the cobalt tetraoxide ferrate fully take respective advantages, on the other hand, the conductivity of the cobalt tetraoxide ferrate is further improved, and therefore the conductivity of the composite cathode material is improved.
In order to improve the comprehensive performance of the composite cathode material, the mass ratio range of the hard carbon, the cobalt tetraoxide ferrite nanowire and the carbon coating layer in the composite cathode material is preferably 20: 10: 1; by setting the mass ratio range of the three components in the range, the capacity of the composite negative electrode material is improved, and meanwhile, the composite negative electrode material has the characteristic of small lithium desorption expansion in the charging and discharging processes, so that the comprehensive performance of the composite negative electrode material is improved.
The composite cathode material provided by the invention takes the hard carbon as a framework, takes the cobalt tetraoxide ferrate nanowire bonded with the hard carbon as a high-capacity provider, and further coats a carbon coating layer on the outer parts of the hard carbon and the cobalt tetraoxide ferrate nanowire, so that the composite cathode material provided by the invention has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of a lithium ion battery on the composite cathode material.
Another object of the present invention is to provide a method for preparing a high capacity type composite anode material, as shown in fig. 3, the method comprising:
s1: mixing citric acid and ethylene glycol to obtain a solution A;
s2: weighing iron salt and cobalt salt, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat to obtain sol C;
s4: adding an alumina molecular sieve into the sol C, stirring at the temperature of 80-120 ℃, and filtering to obtain particles D;
s5: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat to obtain particles E;
s6: dipping the particles E by using an alkali solution, separating insoluble substances, and washing the insoluble substances to be neutral to obtain cobalt tetraoxydipherroate nanowires;
s7: mixing hard carbon with cobalt tetraoxydipherase nano-wires to obtain powder F;
s8: and (3) introducing organic gas into the powder F at the temperature of 800-1200 ℃ to perform chemical vapor deposition to obtain the high-capacity composite anode material.
Firstly, processing raw materials by a sol-gel method, mixing a solution A containing citric acid and glycol with a raw material B containing iron salt and cobalt salt, heating to 120-150 ℃, and carrying out esterification reaction on the citric acid and the glycol to form sol C; the citric acid and the ethylene glycol are used as raw materials, and the iron salt and the cobalt salt are uniformly dispersed in the sol C through the complexing action of the citric acid and the dispersing action of the ethylene glycol, so that the uniformity and the stability of the performance of the composite cathode material are improved.
In order to improve the comprehensive performance of the prepared composite negative electrode material, the mass ratio of citric acid to ethylene glycol in the solution A is preferably 1: 8-1: 4; the ferric salt in the raw material B comprises at least one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferric acetate, ferric citrate, ferrocene, ferrous oxalate, ferric oxalate and ferric phosphate; the cobalt salt comprises at least one of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate and cobalt acetate; the molar ratio of the iron element to the cobalt element in the raw material B is 2: 1-2: 1.2.
In order to fully mix and react the solution A and the raw material B, the raw material B is added into the solution A, stirred and heated to 120-150 ℃, and the temperature is kept, so that the sol C is obtained and comprises the following components: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat for 1-5 hours to obtain sol C; wherein the mass of the solution A is 10-50 times of that of the raw material B.
The preparation method comprises the steps of preparing a cobalt tetraoxide nanowire by a template method, adding an alumina molecular sieve into sol C, stirring at the temperature of 80-120 ℃ by taking the alumina molecular sieve as a template to enable the sol C to fully enter pores of the alumina molecular sieve, filtering, and separating the alumina molecular sieve to obtain particles D, wherein the particles D are the alumina molecular sieve filled with the sol C in the pores.
In order to make the sol C fully enter the pores of the alumina molecular sieve, the alumina molecular sieve is added into the sol C, and the mixture is stirred and filtered at the temperature of 80-120 ℃ to obtain particles D, wherein the particles D comprise: adding an alumina molecular sieve into the sol C, stirring for 1-10 hours at the temperature of 80-120 ℃, and filtering to obtain particles D; wherein the mass of the sol C is 2-10 times of that of the alumina molecular sieve. The alumina molecular sieves of the present invention are preferably commercial alumina molecular sieves.
By using the alumina molecular sieve as a template, on one hand, the pore size of the alumina molecular sieve is uniform and controllable, and the consistency is good, so that the prepared cobalt tetraoxide ferrite nanowire has controllable and uniform size, and the uniformity of the performance of the composite cathode material is improved; on the other hand, the prepared cobalt tetraoxide ferrate is nanocrystallized by taking the alumina molecular sieve as a template, so that the adverse effect caused by volume expansion of the cobalt tetraoxide ferrate in the charge-discharge process can be overcome, the lithium ion migration path is shortened, and the comprehensive performance of the composite cathode material is improved.
In order to further react iron salt and cobalt salt in pores of the alumina molecular sieve to generate cobalt tetraoxide ferrate, adding the particles D into a heating furnace, heating to 400-700 ℃ in an oxidizing atmosphere, preserving heat, allowing the iron salt and the cobalt salt to generate the cobalt tetraoxide ferrate in the pores of the alumina molecular sieve in the oxidizing atmosphere, and allowing the size and the shape of the generated cobalt tetraoxide ferrate to be consistent with those of the pores of the alumina molecular sieve to obtain cobalt tetraoxide ferrate nanowires with uniform size, so as to obtain particles E filled with the cobalt tetraoxide ferrate nanowires in the pores of the alumina molecular sieve; wherein, the particle D is heated to 400-700 ℃ in an oxidizing atmosphere, and the temperature is preserved, so that the obtained particle E comprises: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat for 1-5 hours to obtain particles E; wherein the oxidizing atmosphere comprises at least one of an oxygen atmosphere and an air atmosphere. The heating furnace comprises at least one of a tube furnace, a box furnace, a rotary furnace, a roller furnace, a push plate furnace and a mesh belt furnace.
In order to separate the prepared cobalt tetraoxide ferrate nanowires from the alumina molecular sieve, particles E are soaked by using an alkali solution to dissolve alumina, insoluble substances are separated, and the insoluble substances are washed to be neutral, so that the cobalt tetraoxide ferrate nanowires are obtained.
In order to fully dissolve the alumina, the alkali solution is preferably one or a mixture of strong alkali solution, such as sodium hydroxide solution, potassium hydroxide solution and the like.
According to the invention, the aluminum oxide molecular sieve is used as a template to generate the cobalt ferrate tetroxide nanowire, and then aluminum oxide is dissolved and separated to obtain the uniform and controllable cobalt ferrate tetroxide nanowire, so that the influence on the cycle performance and the rate capability of the composite cathode material due to the agglomeration phenomenon in the preparation process of the cobalt ferrate tetroxide nanowire can be avoided.
In order to form a composite cathode material taking hard carbon as a framework and cobalt tetraoxide ferrate nanowires as a high-capacity provider, mixing the hard carbon with the prepared cobalt tetraoxide ferrate nanowires to obtain powder F; in order to uniformly mix the hard carbon and the cobalt ferrate tetraoxide nanowires, the hard carbon and the cobalt ferrate tetraoxide nanowires are preferably added into a high-speed mixer and mixed for 10-60 min. Wherein the mass ratio of the hard carbon to the cobalt tetraoxydiphosphate nanowire is 2: 1-10: 1; the particle size range of the hard carbon is 5-30 microns. The hard carbon in the present invention is preferably at least one of pitch-based hard carbon, coconut shell carbon, and resin carbon.
In order to increase the connection strength between the hard carbon and the cobalt tetraoxide ferrate nanowire, organic gas is introduced into the powder F at the temperature of 800-1200 ℃ to carry out chemical vapor deposition, the organic gas is pyrolyzed and carbonized in the chemical vapor deposition process, the generated carbon is deposited outside the hard carbon and the cobalt tetraoxide ferrate nanowire, a carbon coating layer is coated outside the hard carbon and the cobalt tetraoxide ferrate nanowire, and the hard carbon and the cobalt tetraoxide ferrate nanowire are bonded to obtain the high-capacity composite cathode material taking the hard carbon as a framework, the cobalt tetraoxide ferrate nanowire as a high-capacity provider and the carbon as the coating layer.
Wherein, the powder F is introduced with organic gas at the temperature of 800-1200 ℃ to carry out chemical vapor deposition, and the obtained high-capacity composite anode material comprises: introducing organic gas into the powder F at the temperature of 800-1200 ℃, and performing chemical vapor deposition for 5-60 minutes to obtain a high-capacity composite anode material; wherein the organic gas comprises at least one of methane, ethane, acetylene, acetone, benzene, toluene, xylene and other organic substances.
According to the preparation method of the high-capacity composite negative electrode material, provided by the invention, the cobalt ferrite tetroxide nanowire is prepared by taking ferric salt and cobalt salt as raw materials and taking an alumina molecular sieve as a template, then hard carbon is mixed with the cobalt ferrite tetroxide nanowire, and a carbon coating layer is prepared outside the hard carbon and the cobalt ferrite tetroxide nanowire, so that the preparation method is simple and the cost is low; the prepared composite negative electrode material has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of the lithium ion battery on the composite negative electrode material.
Still another object of the present invention is to provide a lithium ion battery comprising the above-mentioned high capacity type composite anode material; the advantages of the lithium ion battery are the same as those of the high-capacity composite negative electrode material, and are not described in detail herein.
Example one
The embodiment provides a preparation method of a high-capacity composite anode material, which comprises the following steps:
s1: mixing citric acid and ethylene glycol in a mass ratio of 1:8 to obtain a solution A;
s2: weighing ferric chloride and cobalt chloride with the molar ratio of the iron element to the cobalt element being 2:1, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring to fully dissolve the raw material B, heating to 120 ℃, and preserving heat for 1 hour to obtain sol C, wherein the mass of the solution A is 10 times that of the raw material B;
s4: adding an alumina molecular sieve into the sol C, wherein the mass of the sol C is 2 times that of the alumina molecular sieve, stirring for 1 hour at the temperature of 80 ℃, and filtering to obtain particles D;
s5: putting the particles D into a tube furnace, heating to 400 ℃ in an air atmosphere, and preserving heat for 1 hour to obtain particles E;
s6: soaking the particles E in a sodium hydroxide solution to dissolve the alumina molecular sieve, separating insoluble substances, and washing the insoluble substances to be neutral by deionized water to obtain cobalt tetraoxydipherrite nanowires;
s7: mixing coconut shell-based hard carbon with the particle size of 5 microns and cobalt tetraoxide ferrite nanowires according to the mass ratio of 2:1, adding the mixture into a high-speed mixer, and mixing for 10 minutes to obtain powder F;
s8: and (3) introducing methane gas into the powder F at the temperature of 800 ℃, and carrying out chemical vapor deposition for 5 minutes to obtain the high-capacity composite anode material.
The preparation method of the high-capacity composite anode material provided by the embodiment has the advantages of easily available raw materials, low price, simple preparation process and easy implementation.
Referring to fig. 1, when the high-capacity composite anode material prepared in this embodiment is analyzed, the hard carbon serving as a framework and the cobalt tetraoxide ferrate nanowire serving as a high-capacity provider are coated with a carbon coating layer, so that the composite anode material provided by the invention has the characteristics of high specific capacity, long cycle life, good rate capability, strong processability and good safety performance, and meets the requirements of a lithium ion battery on the composite anode material.
Referring to fig. 2, the cycle life of the high-capacity composite anode material provided in this embodiment is further analyzed, the 1C discharge capacity of the composite anode material reaches 500-.
Example two
The embodiment provides a preparation method of a high-capacity composite anode material, which comprises the following steps:
s1: mixing citric acid and ethylene glycol in a mass ratio of 1:6 to obtain a solution A;
s2: weighing ferrous chloride and cobaltous chloride with the molar ratio of the iron element to the cobalt element being 2:1.1, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring to fully dissolve the raw material B, heating to 140 ℃, and preserving heat for 3 hours to obtain sol C, wherein the mass of the solution A is 30 times that of the raw material B;
s4: adding an alumina molecular sieve into the sol C, wherein the mass of the sol C is 6 times that of the alumina molecular sieve, stirring for 5 hours at the temperature of 100 ℃, and filtering to obtain particles D;
s5: putting the particles D into a box furnace, heating to 500 ℃ in an oxygen atmosphere, and preserving heat for 3 hours to obtain particles E;
s6: soaking the particles E in a potassium hydroxide solution to dissolve the alumina molecular sieve, separating insoluble substances, and washing the insoluble substances to be neutral by deionized water to obtain cobalt tetraoxydipherrite nanowires;
s7: mixing epoxy resin-based hard carbon with the particle size of 20 microns and cobalt tetraoxide ferrite nanowires according to the mass ratio of 6:1, adding the mixture into a high-speed mixer, and mixing for 30 minutes to obtain powder F;
s8: and introducing ethane gas into the powder F at the temperature of 1000 ℃ to perform chemical vapor deposition for 30 minutes to obtain the high-capacity composite anode material.
The preparation method of the high-capacity composite anode material provided by the embodiment has the advantages of easily available raw materials, low price, simple preparation process and easy implementation.
The advantages of the high-capacity composite anode material prepared in this embodiment are the same as those in the first embodiment, and are not described herein again.
EXAMPLE III
The embodiment provides a preparation method of a high-capacity composite anode material, which comprises the following steps:
s1: mixing citric acid and ethylene glycol in a mass ratio of 1:4 to obtain a solution A;
s2: weighing ferric sulfate and cobalt sulfate with the molar ratio of the iron element to the cobalt element being 2:1.2, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring to fully dissolve the raw material B, heating to 150 ℃, and preserving heat for 5 hours to obtain sol C, wherein the mass of the solution A is 30 times that of the raw material B;
s4: adding an alumina molecular sieve into the sol C, wherein the mass of the sol C is 10 times of that of the alumina molecular sieve, stirring for 10 hours at the temperature of 120 ℃, and filtering to obtain particles D;
s5: putting the particles D into a rotary furnace, heating to 700 ℃ in an oxygen atmosphere, and preserving heat for 5 hours to obtain particles E;
s6: soaking the particles E in a potassium hydroxide solution to dissolve the alumina molecular sieve, separating insoluble substances, and washing the insoluble substances to be neutral by deionized water to obtain cobalt tetraoxydipherrite nanowires;
s7: mixing petroleum asphalt-based hard carbon with the particle size of 30 micrometers and cobalt tetraoxide ferrite nanowires according to the mass ratio of 10:1, adding the mixture into a high-speed mixer, and mixing for 60 minutes to obtain powder F;
s8: and introducing acetylene gas into the powder F at the temperature of 1200 ℃ to perform chemical vapor deposition for 60 minutes to obtain the high-capacity composite cathode material.
The preparation method of the high-capacity composite anode material provided by the embodiment has the advantages of easily available raw materials, low price, simple preparation process and easy implementation.
The advantages of the high-capacity composite anode material prepared in this embodiment are the same as those in the first embodiment, and are not described herein again.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a high-capacity composite anode material is characterized by comprising the following steps:
s1: mixing citric acid and ethylene glycol to obtain a solution A;
s2: weighing iron salt and cobalt salt, and mixing to obtain a raw material B;
s3: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat to obtain sol C;
s4: adding an alumina molecular sieve into the sol C, stirring at the temperature of 80-120 ℃, and filtering to obtain particles D;
s5: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat to obtain particles E;
s6: impregnating the particles E with an alkali solution, separating insoluble substances, and washing the insoluble substances to be neutral to obtain cobalt tetraoxydiphosphate nanowires;
s7: mixing hard carbon with the cobalt tetraoxydiphosphate nanowire to obtain powder F;
s8: introducing organic gas into the powder F at the temperature of 800-1200 ℃ to perform chemical vapor deposition to obtain a high-capacity composite anode material;
the high-capacity composite negative electrode material comprises hard carbon, a cobalt tetraoxide ferrite nanowire and a carbon coating layer, wherein the hard carbon is a framework of the high-capacity composite negative electrode material, the cobalt tetraoxide ferrite nanowire is bonded with the hard carbon, and the carbon coating layer is coated outside the hard carbon and the cobalt tetraoxide ferrite nanowire.
2. The method for preparing the high-capacity composite anode material according to claim 1, wherein the mass ratio of the citric acid to the ethylene glycol is in a range of 1:8 to 1: 4.
3. The method for preparing the high-capacity composite anode material according to claim 1, wherein the iron salt includes at least one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferric acetate, ferric citrate, ferrocene, ferrous oxalate, ferric oxalate, and ferric phosphate; the cobalt salt comprises at least one of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate and cobalt acetate; the molar ratio of the iron element to the cobalt element in the raw material B is 2: 1-2: 1.2.
4. The preparation method of the high-capacity composite anode material according to claim 1, wherein the step of adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and keeping the temperature to obtain the sol C comprises the following steps: adding the raw material B into the solution A, stirring, heating to 120-150 ℃, and preserving heat for 1-5 hours to obtain sol C; the mass of the solution A is 10-50 times of that of the raw material B.
5. The preparation method of the high-capacity composite anode material of claim 1, wherein the step of adding an alumina molecular sieve to the sol C, stirring at a temperature of 80-120 ℃, and filtering to obtain particles D comprises: adding the alumina molecular sieve into the sol C, stirring for 1-10 hours at the temperature of 80-120 ℃, and filtering to obtain particles D; wherein the mass of the sol C is 2-10 times of that of the alumina molecular sieve.
6. The preparation method of the high-capacity composite anode material according to claim 1, wherein the step of heating the particles D to 400-700 ℃ in an oxidizing atmosphere and preserving the temperature to obtain the particles E comprises the following steps: heating the particles D to 400-700 ℃ in an oxidizing atmosphere, and preserving heat for 1-5 hours to obtain particles E; wherein the oxidizing atmosphere comprises at least one of an oxygen atmosphere and an air atmosphere.
7. The preparation method of the high-capacity composite anode material according to claim 1, wherein the mass ratio of the hard carbon to the cobalt tetraoxide ferrate nanowire is 2: 1-10: 1; the particle size range of the hard carbon is 5-30 microns.
8. The preparation method of the high-capacity composite anode material according to claim 1, wherein the step of introducing organic gas into the powder F at a temperature of 800-1200 ℃ to perform chemical vapor deposition to obtain the high-capacity composite anode material comprises the following steps: introducing organic gas into the powder F at the temperature of 800-1200 ℃, and performing chemical vapor deposition for 5-60 minutes to obtain a high-capacity composite negative electrode material; wherein the organic gas comprises at least one of methane, ethane, acetylene, acetone, benzene, toluene and xylene organic matters.
9. A high-capacity type composite anode material characterized by being produced by the production method as claimed in claims 1 to 8.
10. A lithium ion battery comprising the high-capacity composite anode material according to claim 9.
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