CN114242978A - Lithium ion battery cathode material, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN114242978A CN114242978A CN202111526296.7A CN202111526296A CN114242978A CN 114242978 A CN114242978 A CN 114242978A CN 202111526296 A CN202111526296 A CN 202111526296A CN 114242978 A CN114242978 A CN 114242978A
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The application provides a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery. The preparation method of the lithium ion battery negative electrode material comprises the following steps: preparing a porous graphite material; establishing an electroplating system, wherein a low-resistance metal material is used as an anode and a porous graphite material is used as a cathode in the electroplating system; electroplating the porous graphite material and the low-resistance metal material to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor to obtain a porous low-resistance anode material sintered body; and grinding and screening the porous low-resistance anode material sintered body to obtain the lithium ion battery anode material. The preparation method of the lithium ion battery cathode material can effectively reduce the resistance of the lithium ion battery cathode material and improve the charging rate of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion power battery is a novel high-energy battery successfully developed in the 20 th century. The negative electrode of this battery is made of a material such as graphite, and the positive electrode is made of lithium iron phosphate, lithium cobaltate, lithium titanate, or the like. The 70 s were put into practical use. It has high energy, high battery voltage, wide working temperature range, long storage life and other advantages, and may be used widely in military and civil small electric appliance.
The negative electrode material of the lithium ion battery is a carrier of lithium ions and electrons in the charging process of the battery, and plays a role in storing and releasing energy. In the cost of the battery, the negative electrode material accounts for about 5% -15%, and is one of important raw materials of the lithium ion battery.
However, most of the conventional lithium ion battery negative electrode materials have the problems of high resistance and long charging time, for example, graphite has low potential, forms an interface film with an electrolyte, and simply forms lithium precipitation; the ion migration speed is slow, so the charge and discharge multiplying power is low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a lithium ion battery cathode material capable of reducing resistance and improving charging rate, a preparation method thereof and a lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
preparing a porous graphite material;
creating an electroplating system in which a low resistance metal material is used as an anode and the porous graphite material is used as a cathode;
electroplating the porous graphite material and the low-resistance metal material to obtain a precursor of the porous low-resistance negative electrode material;
sintering the porous low-resistance anode material precursor to obtain a porous low-resistance anode material sintered body;
and grinding and screening the porous low-resistance anode material sintered body to obtain the lithium ion battery anode material.
In one embodiment, the porous graphite material is prepared by an etching method, a template method, a solvothermal method or a chemical vapor deposition method.
In one embodiment, the template method comprises the steps of:
placing a mesophase pitch feedstock in a mold;
introducing inert gas into the mold, and heating under a preset initial pressure;
and carrying out graphitization operation on the asphalt raw material after the heating operation is finished to obtain the porous graphite material.
In one embodiment, the heating operation comprises the following specific steps:
heating the mesophase pitch raw material to a softening point or higher under high pressure to obtain softened pitch;
after the softened asphalt is obtained, performing pressure relief operation;
and putting the softened asphalt into an oxygen atmosphere for pre-oxidation treatment.
In one embodiment, the low-resistance metal material is at least one of copper and nickel.
In one embodiment, after the step of preparing the porous graphite material and before the step of creating the electroplating system, the method for preparing the lithium ion battery anode material further comprises the following steps:
and carrying out discontinuous cyclone dust removal operation on the porous graphite material.
In one embodiment, after the step of creating an electroplating system and before the step of performing an electroplating operation on the porous graphite material and the low-resistance metal material to obtain a porous low-resistance anode material precursor, the preparation method of the lithium ion battery anode material further includes the following steps:
and carrying out chemical degreasing operation on the porous graphite material.
In one embodiment, after the step of subjecting the porous graphite material and the low-resistance metal material to an electroplating operation to obtain a porous low-resistance anode material precursor, and before the step of subjecting the porous low-resistance anode material sintered body to a grinding and screening operation to obtain the lithium ion battery anode material, the method for preparing the lithium ion battery anode material further comprises the following steps:
and carrying out water washing operation on the porous low-resistance anode material precursor.
A lithium ion battery negative electrode material is prepared by the preparation method of the lithium ion battery negative electrode material according to any one of the embodiments.
A lithium ion battery comprising the lithium ion battery anode material of any of the embodiments above.
Compared with the prior art, the invention has at least the following advantages:
1. according to the preparation method of the lithium ion battery cathode material, the porous graphite material is prepared, and the porous graphite material has a certain porosity and a certain roughness on the surface, so that the adhesion of a low-resistance metal material can be facilitated, and the stability of electroplating operation can be improved; furthermore, the porous graphite material and the low-resistance metal material are subjected to electroplating operation, so that a low-resistance metal coating is formed on the surface of the porous graphite material, the resistance of the porous graphite material is effectively reduced, the conductivity of the porous graphite material is improved, and the porous graphite material is used as a base material of the lithium ion battery negative electrode material, so that the resistance of the lithium ion battery negative electrode material can be effectively reduced, the charging time of the lithium ion battery is effectively shortened, and the rapid charging is realized.
2. According to the preparation method of the lithium ion battery cathode material, the porous graphite material and the low-resistance metal material are subjected to electroplating operation to obtain the porous low-resistance cathode material precursor, and then the porous low-resistance cathode material precursor is subjected to sintering operation, so that the compactness of the porous low-resistance cathode material precursor can be effectively improved, namely the binding force between the porous graphite material and the low-resistance metal material is improved, the conductivity of the lithium ion battery cathode material is further improved, and the charge-discharge rate of the lithium ion battery cathode material is improved.
3. According to the preparation method of the lithium ion battery cathode material, the porous low-resistance cathode material precursor is sintered to obtain the porous low-resistance cathode material sintered body, and then the porous low-resistance cathode material sintered body is ground and screened, so that the uniformity of the porous graphite material and the low-resistance metal material in the porous low-resistance cathode material is effectively improved, the conductivity of the lithium ion battery cathode material is improved, and the stability of the lithium ion battery cathode material is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flowchart of a method for preparing a negative electrode material of a lithium ion battery in an embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The application provides a preparation method of a lithium ion battery cathode material. The preparation method of the lithium ion battery negative electrode material comprises the following steps: preparing a porous graphite material; creating an electroplating system in which a low resistance metal material is used as an anode and the porous graphite material is used as a cathode; electroplating the porous graphite material and the low-resistance metal material to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor to obtain a porous low-resistance anode material sintered body; and grinding and screening the porous low-resistance anode material sintered body to obtain the lithium ion battery anode material.
In the preparation method of the lithium ion battery cathode material, the porous graphite material is prepared, and the porous graphite material has a certain porosity and a certain roughness on the surface, so that the adhesion of a low-resistance metal material can be facilitated, and the stability of electroplating operation can be improved; furthermore, the porous graphite material and the low-resistance metal material are subjected to electroplating operation, so that a low-resistance metal coating is formed on the surface of the porous graphite material, the resistance of the porous graphite material is effectively reduced, the conductivity of the porous graphite material is improved, and the porous graphite material is used as a base material of the lithium ion battery negative electrode material, so that the resistance of the lithium ion battery negative electrode material can be effectively reduced, the charging time of the lithium ion battery is effectively shortened, and the rapid charging is realized. Furthermore, the porous graphite material and the low-resistance metal material are subjected to electroplating operation to obtain a porous low-resistance anode material precursor, and then the porous low-resistance anode material precursor is subjected to sintering operation, so that the compactness of the porous low-resistance anode material precursor can be effectively improved, namely, the binding force between the porous graphite material and the low-resistance metal material is improved, the conductivity of the lithium ion battery anode material is further improved, and meanwhile, the charge-discharge rate of the lithium ion battery anode material is improved. In addition, the porous low-resistance anode material precursor is sintered to obtain a porous low-resistance anode material sintered body, and then the porous low-resistance anode material sintered body is ground and screened, so that the uniformity of a porous graphite material and a low-resistance metal material in the porous low-resistance anode material is effectively improved, the conductivity of the lithium ion battery anode material is improved, and the stability of the lithium ion battery anode material is improved.
In order to better understand the preparation method of the negative electrode material for the lithium ion battery of the present invention, the following further explains the preparation method of the negative electrode material for the lithium ion battery of the present invention, as shown in fig. 1, the preparation method of the negative electrode material for the lithium ion battery of an embodiment includes part or all of the following steps:
s100, preparing the porous graphite material.
It can be understood that the energy density of the lithium ion battery depends on the negative electrode material to a great extent, and the graphite material is a common material for the negative electrode of the lithium ion battery, however, the graphite negative electrode material of the lithium ion battery has the problems of high resistance and long charging time, and the graphite has low porosity and smooth surface, so that the graphite material is not easy to electroplate. In order to improve the stability of the electroplating operation of the lithium ion battery cathode material, in the embodiment, the porous graphite material is prepared by the template method, and the porous graphite material has a certain porosity and a certain roughness on the surface, so that the adhesion of a low-resistance metal material can be facilitated, and the stability of the electroplating operation can be improved.
And S200, creating an electroplating system, wherein the low-resistance metal material is used as an anode, and the porous graphite material is used as a cathode.
It will be appreciated that, in electroplating, the plating metal or other insoluble material acts as the anode and the workpiece to be plated acts as the cathode, and cations of the plating metal are reduced to form a coating on the surface of the workpiece to be plated. In this embodiment, an electroplating system is created, and in the electroplating system, the low-resistance metal material is used as an anode, and the porous graphite material is used as a cathode, so that the effectiveness of an electroplating reaction in the porous graphite material can be ensured, and the low-resistance metal material can form a low-resistance metal layer on the surface of the porous graphite, so that the effectiveness of the electroplating reaction in the porous graphite material is ensured, the doping property of the low-resistance metal material in the porous graphite material is improved, and further the conductivity of the lithium ion battery cathode material is improved.
And S300, carrying out electroplating operation on the porous graphite material and the low-resistance metal material to obtain a precursor of the porous low-resistance negative electrode material.
In this example, a cleaned and specially pretreated porous graphite material was used as a cathode in a plating tank containing an electroplating solution, and a low-resistance metal material was used as an anode, and the anode and the cathode were connected to a positive electrode and a negative electrode of a direct current power supply, respectively. The plating solution is composed of an aqueous solution containing a compound of a low-resistance metal, a conductive salt, a buffer, a pH adjuster, an additive, and the like. After the current is applied, the metal ions in the electroplating solution move to the cathode under the action of the potential difference to form a plating layer. The porous graphite material and the low-resistance metal material are electroplated, so that a low-resistance metal coating is formed on the surface of the porous graphite material, the resistance of the porous graphite material is effectively reduced, the conductivity of the porous graphite material is improved, and the porous graphite material is used as a base material of a lithium ion battery cathode material, so that the resistance of the lithium ion battery cathode material can be effectively reduced, the charging time of the lithium ion battery is effectively shortened, and the rapid charging is realized.
And S400, sintering the porous low-resistance anode material precursor to obtain a porous low-resistance anode material sintered body.
In this embodiment, the porous graphite material and the low-resistance metal material are subjected to an electroplating operation to obtain a porous low-resistance anode material precursor, and then the porous low-resistance anode material precursor is subjected to a sintering operation, so that the compactness of the porous low-resistance anode material precursor can be effectively improved, that is, the binding force between the porous graphite material and the low-resistance metal material is improved, the electrical conductivity of the lithium ion battery anode material is further improved, and the charge-discharge rate of the lithium ion battery anode material is improved.
And S500, grinding and screening the porous low-resistance negative electrode material sintered body to obtain the lithium ion battery negative electrode material.
In this embodiment, a porous low-resistance anode material sintered body is obtained by sintering a porous low-resistance anode material precursor, and then the porous low-resistance anode material sintered body is subjected to a grinding and screening operation, and a ball mill is used to perform a ball milling operation on the porous low-resistance anode material sintered body to obtain a granular porous low-resistance anode material, and then the granular porous low-resistance anode material is screened to obtain a porous low-resistance anode material with uniform granules, so that the uniformity of a porous graphite material and a low-resistance metal material in the porous low-resistance anode material is effectively improved, and the stability of the lithium ion battery anode material is improved while the conductivity of the lithium ion battery anode material is improved.
In one embodiment, the temperature during the sintering operation is 600 ℃ to 800 ℃. It can be understood that if the temperature in the sintering operation is too low, the sintering strength of the porous low-resistance anode material precursor is easily made to be low, and the bonding force between the porous graphite material and the low-resistance metal material is weak, so that the conductivity of the porous low-resistance anode material precursor is weakened, and meanwhile, the low sintering strength of the porous low-resistance anode material precursor is not beneficial to the uniformity of subsequent grinding; if the temperature in the sintering operation is too high, the capacity of the porous low-resistance anode material precursor as an anode material is easily reduced, and even coking may occur. In order to improve the bonding force between the porous graphite material and the low-resistance metal material, in this embodiment, the temperature of the porous low-resistance anode material precursor during sintering is 600 ℃ to 800 ℃, which can effectively improve the bonding force between the porous graphite material and the low-resistance metal material in the porous low-resistance anode material precursor, improve the density and solid brittleness of the sintered body, and prevent the porous low-resistance anode material precursor from being agglomerated in the subsequent grinding process. Further, the time of the sintering operation is 30min to 90 min.
In one embodiment, the grinding and sieving operation comprises in particular the following steps:
and S510, cooling the sinter in an inert gas environment.
In this embodiment, the cooling is performed under an inert gas, so that the high-temperature oxidation of the sinter can be avoided.
S520, putting the cooled sinter into a ball mill to obtain coarse grinding powder; wherein, the working parameters of the ball mill are as follows: the rotation speed is 1000 rpm-1200 rpm, the grinding time is 30 min-60 min, the crystal grains of the porous low-resistance negative electrode material can be suitable, and the structure is compact.
And S530, screening the coarse ground powder to obtain the porous low-resistance negative electrode material. The coarse ground powder is required to be screened to obtain the coarse ground powder with a proper particle size as the porous low-resistance negative electrode material, so that the particle size of the porous low-resistance negative electrode material is ensured to be 4-10 um, and a compact negative electrode material layer can be formed on the copper foil base material.
Through steps S510 to S530, the particle size of the porous low-resistance negative electrode material can be brought into an appropriate range, and a mixture of a dense porous graphite material and a low-resistance metal material is formed, so that a dense negative electrode material layer is formed on the copper foil base material.
In one embodiment, the porous graphite material is prepared by etching, templating, solvothermal or chemical vapor deposition. In this embodiment, the etching method utilizes a chemical reaction between the etchant and the graphite, so that the carbon atoms on the graphite surface are etched by the reaction, and a hole structure is left. The etching method has obvious selectivity for etching the material, and the etching is stopped immediately after the etching is finished, so that the material of the rest layer is not damaged. The template method in this embodiment mainly employs a soft template, which is a supramolecular aggregate, and the soft template in this embodiment is a micelle, an emulsion, a surfactant, a liquid crystal, or a bubble. The self-assembly reaction of the interaction between the carbon precursor and the soft template is carried out, the porous graphite material is obtained through high-temperature carbonization and polymerization, the soft template method is synthesis on the molecular layer, a porous structure is constructed while the interaction of chemical bonds or hydrophilic/hydrophobic acting forces is utilized, the efficiency of preparing the porous graphite material can be effectively improved, and meanwhile, the porosity of the porous graphite material is easy to control. The solvothermal method is to heat water or an organic solvent serving as a reaction system in a preset high-pressure reaction kettle to a critical temperature and synthesize materials in the high-pressure reaction system, so that the method greatly reduces environmental pollution, and the prepared porous graphite material has the advantage of controllable pore diameter. The main process of preparing the porous graphite material by the chemical vapor deposition method is to deposit carbon-containing gas such as methane, acetylene and the like on the surface of a solid matrix to prepare the porous graphite, and then gradually raise the temperature in protective gas to finally obtain the porous graphite material. The method is simple to operate and high in production efficiency, and the prepared porous graphite material is complete in structure and has excellent conductivity.
Further, the template method comprises the following steps:
and S110, placing the mesophase pitch raw material into a mold.
It is understood that the mesophase pitch is a mixture of flat disk-like fused ring aromatic hydrocarbons having a relative molecular mass of 370 to 2000. In the embodiment, the mesophase pitch is used as a raw material for preparing the porous graphite, so that the strength and the thermal conductivity of the porous graphite can be effectively improved; further, the mesophase pitch feed is placed in a mold to facilitate further processing of the mesophase pitch feed.
And S120, introducing inert gas into the mold, and heating at a preset initial pressure.
In this embodiment, the intermediate asphalt material in the mold is pressurized and heated to achieve a softened state, so as to facilitate controllable foaming of the intermediate asphalt material, and obtain uniform porosity. In addition, the above operations are all performed in the state of inert gas, which can protect the pitch intermediate from interference and prevent abnormal reaction from occurring, thereby stabilizing the pitch intermediate reaction.
And S130, performing graphitization operation on the asphalt raw material after the heating operation is completed to obtain the porous graphite material.
It will be appreciated that the foaming of the intermediate asphalt feedstock is completed after the intermediate asphalt feedstock is subjected to a heating operation at a predetermined pressure. In this embodiment, the asphalt raw material after the heating operation is graphitized, and the graphitized asphalt-based foam carbon, that is, the porous graphite material has good high temperature resistance, corrosion resistance and oxidation resistance, and the structure of the porous bubbles is uniform, which is beneficial to improving the uniformity of electroplating of the low-resistance metal material, thereby effectively improving the conductivity of the negative electrode material of the lithium ion battery.
Further, the heating operation comprises the following specific steps:
and S122, heating the mesophase pitch raw material to be above the softening point under high pressure to obtain softened pitch.
In this example, the mesophase pitch is heated at a high pressure to a temperature above the softening point to bring the mesophase pitch to a molten state and to generate a gas during dissolution in order to foam the mesophase pitch by adjusting the pressure to produce a porous structure.
And S124, performing pressure relief operation after obtaining the softened asphalt.
It will be appreciated that the inert gas dissolves in the molten bitumen, i.e. the softened bitumen, after heating the mesophase bitumen feedstock at elevated pressure. In order to further obtain a uniform foamed structure, in this embodiment, after obtaining the softened asphalt, a pressure releasing operation is performed, i.e., the dissolved gas is released by reducing the pressure to foam, so that the softened asphalt generates a uniform foamed structure, which is further beneficial to the electroplating operation of the low-resistance metal material and improves the electroplating uniformity of the low-resistance metal material in the porous graphite.
And S126, placing the softened asphalt into an oxygen atmosphere for pre-oxidation treatment.
It will be appreciated that the expanded structure is created in the intermediate asphalt feedstock after it has been subjected to pressure, heat and pressure release, but the intermediate asphalt feedstock is still in a softened state. In order to further solidify the foaming structure of the intermediate asphalt raw material, in this embodiment, the softened asphalt is put into an oxygen atmosphere for pre-oxidation treatment, so as to further solidify the carbon foam, i.e., the pore structure of the porous graphite precursor, and improve the strength of the pore structure, so that the porous graphite has the advantages of uniform pore diameter, small density, high strength and high thermal conductivity, and is beneficial to electroplating operation of low-resistance metal materials, and the electrical conductivity and stability of the lithium ion battery negative electrode material are improved.
In one embodiment, the low-resistance metal material is at least one of copper and nickel. In the embodiment, the copper has better conductivity, i.e. low resistance, and in addition, the copper also has better abrasion resistance and better process performance, and can be better doped in the porous graphite material through an electroplating mode, so that the resistance of the lithium ion battery cathode material is effectively reduced, and the conductivity of the lithium ion battery cathode material is improved. The nickel has low resistance and good conductivity, the spherical particles of the nickel are in a bead chain shape, and a unique three-dimensional chain structure can form a good conductive network. In addition, the stability of the electroplated nickel layer in the air is very high, and because the metal nickel has very strong passivation capability, a very thin passivation film can be rapidly generated on the surface, so that the corrosion of the atmosphere, alkali and acid in electrolyte can be resisted, the conductivity of the lithium ion battery cathode material is improved, the stability of the lithium ion battery cathode material can be ensured, and the safety of the lithium ion battery is further improved.
In one embodiment, after the step of preparing the porous graphite material and before the step of creating the electroplating system, the method for preparing the lithium ion battery anode material further comprises the steps of: and carrying out discontinuous cyclone dust removal operation on the porous graphite material. It can be understood that after the porous graphite material is prepared, the low-resistance metal material is doped in the porous graphite material through electroplating operation, so that the resistance of the lithium ion battery negative electrode material is reduced, and the conductivity of the lithium ion battery negative electrode material is improved. However, after the porous graphite material is prepared, dust or other impurities are easily left on the surface of the porous graphite material before the plating operation is performed, thereby affecting the plating effect of the low-resistance metal material. In order to improve the tidiness of the porous graphite material before electroplating, in this embodiment, after the step of preparing the porous graphite material and before the step of creating the electroplating system, the preparation method of the lithium ion battery anode material further comprises the following steps: the porous graphite material is subjected to intermittent cyclone dust removal operation, so that dust or other impurities remained on the surface of the porous graphite material are effectively removed, the neatness of the porous graphite material is improved, and the electroplating effect of the low-resistance metal material in the porous graphite material is further improved. It should be noted that, because there are many pore structures in the porous graphite material, when removing dust by blowing, the dust or other impurities on the surface of the porous graphite material are easy to blow into the pores, and because of the continuity and unidirectionality of the wind, the wind can not break away the dust and other impurities from the pore structures.
In one embodiment, the method for preparing the negative electrode material of the lithium ion battery after the step of creating the electroplating system and before the step of performing the electroplating operation on the porous graphite material and the low-resistance metal material to obtain the precursor of the porous low-resistance negative electrode material further comprises the following steps: and carrying out chemical degreasing operation on the porous graphite material. It can be understood that if organic substances such as oil stains exist on the surface of the to-be-plated part, namely the porous graphite material, during electroplating, the flatness, the bonding force and the corrosion resistance of an electroplated layer are easily affected by the oil stain interlayer, and even the problems of discontinuous deposition, looseness and even peeling of the electroplated layer occur. In order to effectively remove oil stains and other organic substances on the surface of the porous graphite material and improve the stability of the electroplating operation, in this embodiment, the preparation method of the negative electrode material for the lithium ion battery, after the step of creating the electroplating system and before the step of performing the electroplating operation on the porous graphite material and the low-resistance metal material to obtain the precursor of the porous low-resistance negative electrode material, further includes the following steps: the method comprises the following steps of carrying out chemical degreasing operation on a porous graphite material, specifically, placing the porous graphite material in heated chemical degreasing liquid for immersion cleaning or boiling after the porous graphite material is hung or small pieces are contained by a basket and the like, so that oil stains and other organic substances in the porous graphite material can be effectively removed, and the stability of electroplating operation is further improved.
In one embodiment, after the step of subjecting the porous graphite material and the low-resistance metal material to an electroplating operation to obtain the porous low-resistance anode material precursor, and before the step of subjecting the porous low-resistance anode material sintered body to a grinding and screening operation to obtain the lithium ion battery anode material, the preparation method of the lithium ion battery anode material further comprises the following steps: and (4) carrying out water washing operation on the porous low-resistance anode material precursor. It can be understood that after the porous graphite material and the low-resistance metal material are subjected to electroplating operation, a porous low-resistance negative electrode material precursor is obtained, electroplating solution is easy to remain after the porous low-resistance negative electrode material precursor is plated out of the electroplating bath, and if the porous low-resistance negative electrode material precursor is not cleaned in time, a plating layer in the porous low-resistance negative electrode material precursor is easy to discolor or rusty spots and white spots appear, so that the quality of the porous low-resistance negative electrode material precursor is influenced, and even the conductivity of the lithium ion battery negative electrode material is influenced. In order to improve the stability of the precursor of the porous low-resistance anode material, in this embodiment, after the step of performing an electroplating operation on the porous graphite material and the low-resistance metal material to obtain the precursor of the porous low-resistance anode material, and before the step of performing a grinding and screening operation on the sintered body of the porous low-resistance anode material to obtain the anode material of the lithium ion battery, the preparation method of the anode material of the lithium ion battery further includes the following steps: and (3) carrying out water washing operation on the porous low-resistance anode material precursor, thereby effectively removing residual electroplating solution in the porous low-resistance anode material precursor.
Furthermore, in the process of water washing operation, the porous low-resistance anode material precursor is rotated, because the porous low-resistance anode material precursor has more pore structures, the problem that the residual electroplating solution in the pore structures is easy to have cleaning dead angles and cannot be cleaned thoroughly is solved, and if an ultrasonic or oscillation cleaning mode is adopted, the electroplated layer in the porous low-resistance anode material precursor is easy to damage, so that the conductivity of the porous low-resistance anode material precursor is influenced; in this embodiment, the porous low-resistance anode material precursor is rotated, so that the porous low-resistance anode material precursor can move relative to the washing solution in the washing process, and the residual electroplating solution in the pore structure can be sufficiently taken away by the washing solution flowing repeatedly in the pore structure. And through carrying out the rotation operation to porous low resistance anode material precursor, rather than controlling the frequency of washing, can control the impact force between porous low resistance anode material precursor and the washing liquid better to when fully rinsing remaining plating solution in porous low resistance anode material precursor, can also guarantee the stability between plating layer and the porous graphite in the porous low resistance anode material precursor, thereby guarantee the electric conductivity and the stability of porous low resistance anode material precursor.
Some specific examples are listed below, and if mentioned%, all are expressed in weight percent. It should be noted that the following examples are not intended to be exhaustive of all possible cases, and that the materials used in the following examples are commercially available without specific recitation.
Example 1
Firstly, preparing a porous graphite material by a template method; then, an electroplating system is established, wherein in the electroplating system, a low-resistance metal material is used as an anode, and a porous graphite material is used as a cathode; then placing the porous graphite material and the low-resistance metal material into a plating tank containing electroplating solution to carry out electroplating operation to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor, wherein the sintering temperature is 600 ℃, and the sintering time is 30min, so as to obtain a porous low-resistance anode material sintered body; and finally, putting the cooled porous low-resistance anode material sintered body into a ball mill, and carrying out grinding and screening operation on the porous low-resistance anode material sintered body, wherein the working parameters of the ball mill are as follows: the rotating speed is 1000rpm, and the grinding time is 30min, so that the lithium ion battery cathode material is obtained.
Example 2
Firstly, preparing a porous graphite material by a template method; then, an electroplating system is established, wherein in the electroplating system, a low-resistance metal material is used as an anode, and a porous graphite material is used as a cathode; then placing the porous graphite material and the low-resistance metal material into a plating tank containing electroplating solution to carry out electroplating operation to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor, wherein the sintering temperature is 800 ℃, and the sintering time is 90min, so as to obtain a porous low-resistance anode material sintered body; and finally, putting the cooled porous low-resistance anode material sintered body into a ball mill, and carrying out grinding and screening operation on the porous low-resistance anode material sintered body, wherein the working parameters of the ball mill are as follows: the rotating speed is 1200rpm, and the grinding time is 60min, so that the lithium ion battery cathode material is obtained.
Example 3
Firstly, preparing a porous graphite material by a template method; then, an electroplating system is established, wherein in the electroplating system, a low-resistance metal material is used as an anode, and a porous graphite material is used as a cathode; then placing the porous graphite material and the low-resistance metal material into a plating tank containing electroplating solution to carry out electroplating operation to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor, wherein the sintering temperature is 700 ℃, and the sintering time is 60min, so as to obtain a porous low-resistance anode material sintered body; and finally, putting the cooled porous low-resistance anode material sintered body into a ball mill, and carrying out grinding and screening operation on the porous low-resistance anode material sintered body, wherein the working parameters of the ball mill are as follows: the rotating speed is 1100rpm, and the grinding time is 40min, so that the lithium ion battery cathode material is obtained.
Example 4
Firstly, preparing a porous graphite material by a template method; then, an electroplating system is established, wherein in the electroplating system, a low-resistance metal material is used as an anode, and a porous graphite material is used as a cathode; then placing the porous graphite material and the low-resistance metal material into a plating tank containing electroplating solution to carry out electroplating operation to obtain a precursor of the porous low-resistance negative electrode material; sintering the porous low-resistance anode material precursor, wherein the sintering temperature is 650 ℃, and the sintering time is 80min, so as to obtain a porous low-resistance anode material sintered body; and finally, putting the cooled porous low-resistance anode material sintered body into a ball mill, and carrying out grinding and screening operation on the porous low-resistance anode material sintered body, wherein the working parameters of the ball mill are as follows: the rotating speed is 1000rpm, and the grinding time is 35min, so that the lithium ion battery cathode material is obtained.
The application also provides a lithium ion battery cathode material, which is prepared by the preparation method of the lithium ion battery cathode material according to any one of the embodiments.
The application also provides a lithium ion battery, which comprises the lithium ion battery negative electrode material in any embodiment.
Compared with the prior art, the invention has at least the following advantages:
1. according to the preparation method of the lithium ion battery cathode material, the porous graphite material is prepared, and the porous graphite material has a certain porosity and a certain roughness on the surface, so that the adhesion of a low-resistance metal material can be facilitated, and the stability of electroplating operation can be improved; furthermore, the porous graphite material and the low-resistance metal material are subjected to electroplating operation, so that a low-resistance metal coating is formed on the surface of the porous graphite material, the resistance of the porous graphite material is effectively reduced, the conductivity of the porous graphite material is improved, and the porous graphite material is used as a base material of the lithium ion battery negative electrode material, so that the resistance of the lithium ion battery negative electrode material can be effectively reduced, the charging time of the lithium ion battery is effectively shortened, and the rapid charging is realized.
2. According to the preparation method of the lithium ion battery cathode material, the porous graphite material and the low-resistance metal material are subjected to electroplating operation to obtain the porous low-resistance cathode material precursor, and then the porous low-resistance cathode material precursor is subjected to sintering operation, so that the compactness of the porous low-resistance cathode material precursor can be effectively improved, namely the binding force between the porous graphite material and the low-resistance metal material is improved, the conductivity of the lithium ion battery cathode material is further improved, and the charge-discharge rate of the lithium ion battery cathode material is improved.
3. According to the preparation method of the lithium ion battery cathode material, the porous low-resistance cathode material precursor is sintered to obtain the porous low-resistance cathode material sintered body, and then the porous low-resistance cathode material sintered body is ground and screened, so that the uniformity of the porous graphite material and the low-resistance metal material in the porous low-resistance cathode material is effectively improved, the conductivity of the lithium ion battery cathode material is improved, and the stability of the lithium ion battery cathode material is improved.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the lithium ion battery negative electrode material is characterized by comprising the following steps of:
preparing a porous graphite material;
creating an electroplating system in which a low resistance metal material is used as an anode and the porous graphite material is used as a cathode;
electroplating the porous graphite material and the low-resistance metal material to obtain a precursor of the porous low-resistance negative electrode material;
sintering the porous low-resistance anode material precursor to obtain a porous low-resistance anode material sintered body;
and grinding and screening the porous low-resistance anode material sintered body to obtain the lithium ion battery anode material.
2. The preparation method of the lithium ion battery negative electrode material according to claim 1, wherein the porous graphite material is prepared by an etching method, a template method, a solvothermal method or a chemical vapor deposition method.
3. The preparation method of the lithium ion battery anode material according to claim 2, wherein the template method comprises the following steps:
placing a mesophase pitch feedstock in a mold;
introducing inert gas into the mold, and heating under a preset initial pressure;
and carrying out graphitization operation on the asphalt raw material after the heating operation is finished to obtain the porous graphite material.
4. The preparation method of the lithium ion battery anode material according to claim 3, wherein the heating operation comprises the following specific steps:
heating the mesophase pitch raw material to a softening point or higher under high pressure to obtain softened pitch;
after the softened asphalt is obtained, performing pressure relief operation;
and putting the softened asphalt into an oxygen atmosphere for pre-oxidation treatment.
5. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the low-resistance metal material is at least one of copper and nickel.
6. The method for preparing a negative electrode material for a lithium ion battery according to claim 1, wherein after the step of preparing the porous graphite material and before the step of creating the plating system, the method for preparing a negative electrode material for a lithium ion battery further comprises the steps of:
and carrying out discontinuous cyclone dust removal operation on the porous graphite material.
7. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein after the step of creating the electroplating system and before the step of subjecting the porous graphite material and the low-resistance metal material to the electroplating operation to obtain the precursor of the porous low-resistance negative electrode material, the method for preparing the negative electrode material of the lithium ion battery further comprises the following steps:
and carrying out chemical degreasing operation on the porous graphite material.
8. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein after the step of subjecting the porous graphite material and the low-resistance metal material to the plating operation to obtain the precursor of the porous low-resistance negative electrode material and before the step of subjecting the sintered body of the porous low-resistance negative electrode material to the grinding and sieving operation to obtain the negative electrode material for the lithium ion battery, the method further comprises the steps of:
and carrying out water washing operation on the porous low-resistance anode material precursor.
9. The lithium ion battery negative electrode material is characterized by being prepared by the preparation method of the lithium ion battery negative electrode material according to any one of claims 1 to 8.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery negative electrode material according to claim 9.
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