CN106941167B - Porous composite negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Porous composite negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a porous composite negative electrode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of electrode materials of lithium ion batteries. The preparation method comprises the following steps: (1) uniformly mixing a porous graphite material, a conductive agent, a polymer and a pore-forming agent in a solvent to obtain an electrospinning solution; (2) carrying out electrospinning on the electrospinning liquid to prepare composite fibers; (3) under the protection of inert gas, firstly, the composite fiber is insulated for 1 hour at 300 ℃, then calcined for 0.5 to 15 hours at the temperature of 1000 to 1500 ℃, and then cooled to room temperature, thus obtaining the composite fiber, or firstly, the composite fiber is insulated for 1 to 2 hours at the temperature of 300 to 320 ℃, then calcined for 0.5 to 15 hours at the temperature of 1000 to 1500 ℃, cooled, added with a chemical corrosive to remove a pore-forming agent, dried and cooled, thus obtaining the composite fiber. The porous composite negative electrode material prepared by the invention has good rate performance and meets the performance requirement of lithium ion rapid charging.
Description
Technical Field
The invention relates to a porous composite negative electrode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of electrode materials of lithium ion batteries.
Background
With the industrial development and the widening of the application field of the lithium ion battery, higher requirements are put forward for the power density and the energy density of the lithium ion battery, and the requirements of quick charge and discharge and long endurance life of the lithium ion battery are particularly urgent. The negative electrode material is used as a key material influencing the quick charge of the lithium ion battery, and the effective way for solving the problems is to ensure the high capacity of the negative electrode material and improve the quick charge performance of the negative electrode material at the same time.
In the charging process of the conventional graphite cathode material, lithium ions are embedded into graphite from the edge of a graphite layer in a direction parallel to the graphite layer, the distance reaching the deep part in the graphite layer is long, and the large-rate charging performance of the graphite cathode material is limited by a small diffusion coefficient. In addition, when the prepared battery is repeatedly charged with a large multiplying power, the graphite flake is very easy to peel off due to repeated and rapid expansion and contraction of the negative electrode material, the number of joints among material particles is reduced, a conductive network in an electrode is damaged, in addition, the high-pressure compaction design for ensuring the energy density causes the reduction of material gaps, the penetration of electrolyte is difficult, the increase of electrode polarization in the high-multiplying power charging process is easily caused, and finally the cycle performance of the battery is deteriorated.
Chinese patent (application publication No. CN 105932320A, application publication date: 2016.09.07) discloses a method for preparing a composite anode material by graphite modification, and specifically discloses the following contents: the preparation method comprises four processes of solution A preparation, solution B preparation, solution C preparation and composite negative electrode material preparation, wherein a polymer matrix, a pore-forming agent, a conductive agent, an inorganic additive and an organic solvent are used in the solution A preparation process, asphalt and an organic solvent are used in the solution B preparation process, the solution A and the solution B are used in the solution C preparation process, finally, the composite negative electrode material preparation is carried out, graphite is added into a three-dimensional mixer and is added with the solution C for stirring, the temperature rise rate of the three-dimensional mixer is controlled to be 2-10 ℃/min and is heated to 100-160 ℃ during stirring, the rotating speed of the three-dimensional mixer is controlled to be 100-150 rpm and is stirred for 1.0-10 h, then, the temperature is raised to 600-1000 ℃ and is kept for 6-24 h, and finally, the temperature is lowered under the protection of inert gas. Although the application applies the pore-forming technology and the doping modification technology to modify graphite, the capacity, the specific surface area and the conductivity of the prepared composite negative electrode material are improved, but the requirements of production and life, especially the requirement of quick charging, cannot be met.
Disclosure of Invention
In order to overcome the defect of poor quick charging performance of the conventional lithium ion battery cathode material, the first object of the invention is to provide a preparation method of a porous composite cathode material for quick charging; the second purpose of the invention is to provide a fast-charging porous composite anode material directly prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a porous composite anode material of a lithium ion battery comprises the following steps:
(1) uniformly mixing a porous graphite material, a conductive agent, a polymer and a first pore-forming agent in a solvent to obtain an electrospinning solution;
(2) carrying out electrospinning on the electrospinning liquid to prepare composite fibers;
(3) under the protection of inert gas, firstly, insulating the composite fiber at 300-320 ℃ for 1-2 h, then calcining at 1000-1500 ℃ for 0.5-15 h, decomposing at high temperature to remove a pore-forming agent, and cooling to obtain the composite fiber;
or
(a) Uniformly mixing a porous graphite material, a conductive agent, a polymer and a second pore-forming agent in a solvent to obtain an electrospinning solution;
(b) carrying out electrospinning on the electrospinning liquid to prepare composite fibers;
(c) the composite fiber is firstly insulated for 1-2 h at 300-320 ℃, then calcined for 0.5-15 h at 1000-1500 ℃, cooled, added with a chemical corrosive to remove a pore-forming agent, dried and cooled to obtain the composite fiber.
The mass ratio of the porous graphite material, the conductive agent, the polymer and the first pore-forming agent in the step (1) is as follows: (10-30): (0.1-7): (8-30): (5-15); the mass ratio of the porous graphite material, the conductive agent, the polymer and the second pore-forming agent in the step (a) is as follows: (10-30): (0.1-7): (8-30): (5-15).
Further preferably, the mass ratio of the porous graphite material, the conductive agent, the polymer, the pore-forming agent and the solvent in the electrospinning solution is as follows: (10-30): (0.1-7): (8-30): (5-15): (100).
The solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethylene carbonate and dimethyl furan, but is not limited thereto.
In the preparation method of the porous composite negative electrode material of the lithium ion battery, the used porous graphite material is formed by impregnating graphite with alkali metal or alkali metal alkaline aqueous solution and performing heat treatment on the separated graphite.
In the preparation method of the porous composite negative electrode material of the lithium ion battery, the porous graphite material is one or the composition of more than two of artificial graphite, natural graphite and mesocarbon microbeads with porous structures.
In the preparation method of the porous composite anode material of the lithium ion battery, the average particle diameter D of the porous graphite material50Is 3 to 15 μm.
In the preparation method of the porous composite anode material of the lithium ion battery, the preparation method of the porous graphite material comprises the following steps: soaking artificial graphite, natural graphite, mesocarbon microbeads or a combination of more than two of the artificial graphite, the natural graphite and the mesocarbon microbeads in an alkaline aqueous solution for 5min to 48h, controlling the soaking temperature to be 20 ℃ to 60 ℃, then carrying out heat treatment for 0.5h to 48h at 500 ℃ to 1200 ℃ under the protection of inert gas, washing with water and drying to obtain the nano-graphite.
The alkaline aqueous solution is NaOH aqueous solution, KOH aqueous solution and the like.
The concentration of the alkaline aqueous solution is preferably 0.05M to 15M.
In the preparation method of the porous composite cathode material of the lithium ion battery, the first pore-forming agent is an organic pore-forming agent; the second pore-forming agent is an oxide pore-forming agent. Adding pore-forming agent into the electrospinning liquid, preparing composite fiber through electrospinning, and then removing the pore-forming agent in the composite fiber through thermal decomposition, solvent in organic solvent or chemical corrosion, thereby forming holes in the composite fiber, increasing the porosity of the negative electrode material, increasing the passage of lithium ions into and out of graphite, shortening the diffusion distance of the lithium ions between graphite layers, and improving the transmission efficiency of the lithium ions in the graphite.
The organic pore-forming agent is one of polystyrene, polyvinyl alcohol, polyethylene, polyvinyl acetate and polymethyl methacrylate.
The oxide pore-forming agent is one of silicon dioxide, titanium dioxide, zinc oxide and copper oxide.
The chemical corrosive is one of hydrochloric acid with the mass fraction of 5-20%, sulfuric acid with the mass fraction of 5-20%, hydrofluoric acid with the mass fraction of 5-15% and sodium hydroxide solution with the mass fraction of 20-60%.
In the preparation method of the porous composite cathode material for the lithium ion battery, the conductive agent is one or more than two composite materials of acetylene black, conductive carbon black, carbon nano tubes, nitrogen-doped carbon nano tubes, graphene, nitrogen-doped graphene and carbon fibers.
In the preparation method of the porous composite cathode material of the lithium ion battery, the polymer is at least one of polyacrylonitrile, polyaniline, polypyrrole and polyimide.
In the preparation method of the porous composite anode material for the lithium ion battery, the technical parameters of the electrospinning are as follows: voltage: 5-20 KV, the speed of electrospinning is 10-20 muL/min, and the distance between motors is 15-20 cm.
The porous composite negative electrode material of the lithium ion battery prepared by the preparation method.
According to the porous composite negative electrode material provided by the invention, on one hand, the porous structure increases the passage of lithium ions entering and exiting the graphite layer, the diffusion distance of the lithium ions between the graphite layers is shortened, the rapid penetration of electrolyte is facilitated, the liquid absorption performance of the material is improved, the polarization in the rapid charging process is reduced, and the volume expansion of graphite during charging is relieved, and on the other hand, the introduced conductive agent increases the conductivity of the graphite, so that the negative electrode material provided by the invention has good rate capability, and the requirement of high-rate charging performance of a lithium ion battery is met.
Drawings
Fig. 1 is a schematic structural diagram of a porous composite negative electrode material in example 1, where 1 is a porous carbon material, 2 is a conductive agent, and 3 is a carbon fiber soft carbon layer.
Detailed Description
The present invention will be described in further detail with reference to examples. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Example 1
The schematic structural diagram of the porous composite anode material in this embodiment is shown in fig. 1, where 1 is a porous carbon material, 2 is a conductive agent, and 3 is a carbon fiber soft carbon layer.
The preparation method of the porous composite anode material of the porous lithium ion battery comprises the following steps:
1) preparing a porous graphite material: the average particle diameter D is adjusted at room temperature of 25 DEG C5010 μm, a specific surface area of 1.2m2Soaking the artificial graphite powder in 5M KOH aqueous solution for 10 hours; then separating graphite powder by vacuum filtration, treating for 2 hours at 800 ℃ in an argon atmosphere, washing the graphite powder by deionized water, and finally drying for 36 hours at 60 ℃ to obtain porous artificial graphite;
2) preparation of the electrospinning solution: uniformly dispersing 5 parts of polymethyl methacrylate, 10 parts of polyacrylonitrile, 0.1 part of carbon nano tube and 10 parts of porous artificial graphite in 100 parts of N, N-dimethylformamide to obtain the composite material;
3) preparing a porous composite negative electrode material: under the condition of room temperature of 25 ℃, carrying out electrospinning on the electrospinning solution at the voltage of 15kV and the speed of 1mL/h to prepare composite fibers, wherein the distance between electrodes is 20cm, and aluminum foils are used as collecting electrodes; heating the composite fiber to 300 ℃ at a speed of 1.5 ℃/min in a furnace, keeping the temperature for 1h, then heating to 1100 ℃ at a speed of 2.5 ℃/h, keeping the temperature for 3h, and cooling to room temperature to obtain the porous composite material; argon is introduced as protective atmosphere in the whole calcining process.
Example 2
In this example, 0.5 part of carbon nanotubes was used in step 2), and the rest was the same as in example 1.
Example 3
1) Preparing a porous graphite material: the average particle diameter D is adjusted at room temperature of 25 DEG C5010 μm, a specific surface area of 1.2m2Soaking the artificial graphite powder in 5M KOH aqueous solution for 10 hours; then separating graphite powder by vacuum filtration, treating for 2 hours at 800 ℃ in an argon atmosphere, washing the graphite powder by deionized water, and finally drying for 36 hours at 60 ℃ to obtain porous artificial graphite;
2) preparation of the electrospinning solution:dissolving 10 parts of polyacrylonitrile in 100 parts of N, N-dimethylformamide, and sequentially weighing 0.3 part of carbon nanotube, 15 parts of porous artificial graphite and 5 parts of SiO2Ultrasonically uniformly dispersing in a solution, wherein SiO2The diameter of the nano particles is 50 nm;
3) preparing a porous composite negative electrode material: under the condition of room temperature and 25 ℃, carrying out electrospinning on the electrospinning solution at the voltage of 12kV and the speed of 1mL/h to prepare composite fibers, wherein the distance between electrodes is 18cm, and aluminum foil is used as a collecting electrode; heating the composite fiber to 300 ℃ at a speed of 1.5 ℃/min in a furnace, keeping the temperature for 1h, then heating to 1100 ℃ at a speed of 2.5 ℃/h, keeping the temperature for 3h, and cooling to room temperature to obtain SiO2a/C fiber. And (3) soaking the composite fiber in a concentrated NaOH solution (with the concentration of 20-60%) for 10 hours, washing the composite fiber with deionized water until the composite fiber is neutral, and drying the composite fiber to obtain the porous composite anode material.
Example 4
1) Preparing a porous graphite material: the average particle diameter D is adjusted at room temperature of 25 DEG C50Is 12 μm and has a specific surface area of 2.5m2Soaking the natural graphite powder in 2M NaOH aqueous solution for 12 hours; then separating the graphite powder by vacuum filtration, treating for 1 hour (temperature 900 ℃) in an argon atmosphere, washing the graphite powder by deionized water, and finally drying for 40 hours at 50 ℃ to obtain porous natural graphite;
2) preparation of the electrospinning solution: uniformly dispersing 6 parts of polymethyl methacrylate, 12 parts of polyacrylonitrile, 0.5 part of carbon nano tube and 11.5 parts of porous natural graphite in 100 parts of N, N-dimethyl formamide to obtain the nano-composite material.
3) Preparing a porous composite negative electrode material: under the condition of room temperature and 25 ℃, carrying out electrospinning on the electrospinning solution at the voltage of 13kV and the speed of 1.3mL/h to prepare composite fibers, wherein the distance between electrodes is 15cm, and aluminum foils are used as collecting electrodes; heating the composite fiber in a furnace at 2 ℃/min to 320 ℃ for 2h, then heating to 1000 ℃ at 3 ℃/h for 4h, and cooling to room temperature to obtain the porous composite material; argon is introduced as protective atmosphere in the whole calcining process.
Example 5
In step 2) of this example, the same mass of graphene was used instead of carbon nanotubes, and the rest was the same as in example 1.
Example 6
1) Preparing a porous graphite material: the average particle diameter D is adjusted at room temperature of 25 DEG C50Is 12 μm and has a specific surface area of 2.5m2Soaking the natural graphite powder in 2M NaOH aqueous solution for 12 hours; then separating the graphite powder by vacuum filtration, treating for 1 hour (temperature 900 ℃) in an argon atmosphere, washing the graphite powder by deionized water, and finally drying for 40 hours at 50 ℃ to obtain porous natural graphite;
2) preparation of the electrospinning solution: uniformly dispersing 15 parts of polymethyl methacrylate, 30 parts of polyacrylonitrile, 7 parts of carbon nano tube and 30 parts of porous natural graphite in 100 parts of N, N-dimethyl formamide to obtain the composite material.
3) Preparing a porous composite negative electrode material: under the condition of room temperature and 25 ℃, carrying out electrospinning on the electrospinning solution at the voltage of 13kV and the speed of 1.3mL/h to prepare composite fibers, wherein the distance between electrodes is 15cm, and aluminum foils are used as collecting electrodes; heating the composite fiber in a furnace at 2 ℃/min to 320 ℃ for 2h, then heating to 1000 ℃ at 3 ℃/h for 4h, and cooling to room temperature to obtain the porous composite material; argon is introduced as protective atmosphere in the whole calcining process.
Example 7
1) Preparing a porous graphite material: the average particle diameter D is adjusted at room temperature of 25 DEG C50Is 12 μm and has a specific surface area of 2.5m2Soaking the natural graphite powder in 2M NaOH aqueous solution for 12 hours; then separating the graphite powder by vacuum filtration, treating for 1 hour (temperature 900 ℃) in an argon atmosphere, washing the graphite powder by deionized water, and finally drying for 40 hours at 50 ℃ to obtain porous natural graphite;
2) preparation of the electrospinning solution: uniformly dispersing 5 parts of polymethyl methacrylate, 8 parts of polyacrylonitrile, 0.5 part of carbon nano tube and 10 parts of porous natural graphite in 100 parts of N, N-dimethyl formamide to obtain the composite material.
3) Preparing a porous composite negative electrode material: under the condition of room temperature and 25 ℃, carrying out electrospinning on the electrospinning solution at the voltage of 13kV and the speed of 1.3mL/h to prepare composite fibers, wherein the distance between electrodes is 15cm, and aluminum foils are used as collecting electrodes; heating the composite fiber in a furnace at 2 ℃/min to 320 ℃ for 2h, then heating to 1000 ℃ at 3 ℃/h for 4h, and cooling to room temperature to obtain the porous composite material; argon is introduced as protective atmosphere in the whole calcining process.
Comparative example 1
In this comparative example, a composite negative electrode material was prepared using the same artificial graphite powder as in example 1 as the raw material, the artificial graphite powder having an average particle diameter D5010 μm, a specific surface area of 1.2m2(ii)/g; the artificial graphite powder is not treated in the step 1) of the embodiment 1 in the preparation process, and the preparation methods for preparing the electrospinning solution and the composite negative electrode material are the same as the embodiment 1.
Comparative example 2
A porous graphite material, which is a negative electrode material, was prepared in the same manner as in step 1) of example 1.
Test examples
The negative electrode materials in examples 1 to 3 and comparative examples 1 and 2 were tested for discharge capacity, first efficiency, and fast charge performance by the button cell test method, and the results are shown in table 1.
The button cell testing method used by the invention comprises the following steps: and adding conductive carbon black into the LA132 aqueous solution, then adding a graphite sample, uniformly stirring, and uniformly coating the mixture on the surface of copper foil to prepare the pole piece. And (3) putting the coated pole piece into a vacuum drying oven at 100 ℃ for vacuum drying for 6h, taking out the pole piece, and rolling the pole piece on a roller press for later use. The button cell is assembled in a glove box filled with Ar gas, and the electrolyte is 1.2MLiPF6And EC, DMC is 1:1:1 (volume ratio), and the metal lithium sheet is used as a counter electrode. The capacity test was performed on a blue tester.
The button cell testing process comprises the following steps: firstly, charging to 0.005V at 0.1C, standing for 5 minutes, discharging to 2.5V at 0.1C, and circulating twice; charged to 0.005V at 6C and left for 5 minutes.
8 button cells were tested in parallel at 25 ℃. + -. 2 ℃ and the values were averaged after removal of outliers (according to GB4883-1985, when the value exceeds twice the standard deviation of the mean value, the value is an outlier). The gram capacity of the anode material was calculated using the following formula:
C＝Cavepercent of active material/[ (M electrode-M copper foil) × (M.times.)]
Wherein C: the gram capacity of the negative electrode material mAh/g; cave: average discharge capacity mAh of the button cell; m electrode: weight g of the negative plate; m copper foil: weight g of copper foil.
TABLE 1 button cell test
The method comprises the steps of soaking the graphite carbon material in an alkaline aqueous solution, and then carrying out heat treatment to form certain stripping oxidation among carbon layers of the carbon material, so that certain structural defects are caused, the specific surface area of the carbon material is increased, the conductive agent, the polymer and the pore-forming agent are favorably in full contact with the carbon material, and the components are uniformly distributed. The composite fiber is prepared through electrospinning, and the components of the prepared composite fiber are uniformly distributed, so that the composite anode material with uniformly distributed holes and uniform pore diameter is formed in the subsequent pore-forming process. And finally, removing the pore-forming agent by calcining or calcining and adding a chemical corrosive agent to process so as to obtain the composite cathode material. In the calcining process, the defects on the carbon material can be removed by high treatment temperature, such as removing some oxygen-containing functional groups and carbon layer edge incomplete structures, so that the conductivity of the material is improved.
The composite negative electrode material prepared by the invention has uniform pore size distribution and higher specific surface area, provides a good transmission channel for the transmission of lithium ions, is beneficial to the transmission of the lithium ions, and has fewer defects, high conductivity and good structural stability. Through the button cell test, the good structure and the high specific surface area of the button cell can accept and transmit more lithium ions, so that the initial capacity of the button cell is obviously higher than that of the comparative example, and through a charge rate characteristic test, the composite negative electrode material disclosed by the invention is stable in structure, less in defects and high in capacity retention rate. The porous carbon composite negative electrode material prepared by the method has excellent electrochemical performance, and particularly has excellent rate performance.
Claims (8)
1. A preparation method of a porous composite anode material of a lithium ion battery is characterized by comprising the following steps:
(1) uniformly mixing a porous graphite material, a conductive agent, a polymer and a first pore-forming agent in a solvent to obtain an electrospinning solution;
(2) carrying out electrospinning on the electrospinning liquid to prepare composite fibers;
(3) under the protection of inert gas, firstly, insulating the composite fiber at 300-320 ℃ for 1-2 h, then calcining at 1000-1500 ℃ for 0.5-15 h, decomposing at high temperature to remove a pore-forming agent, and cooling to obtain the composite fiber;
or
(a) Uniformly mixing a porous graphite material, a conductive agent, a polymer and a second pore-forming agent in a solvent to obtain an electrospinning solution;
(b) carrying out electrospinning on the electrospinning liquid to prepare composite fibers;
(c) firstly, the composite fiber is subjected to heat preservation for 1-2 hours at the temperature of 300-320 ℃, then is calcined for 0.5-15 hours at the temperature of 1000-1500 ℃, is cooled, is added with a chemical corrosive to remove a pore-forming agent, is dried and is cooled to obtain the composite fiber;
the mass ratio of the porous graphite material, the conductive agent, the polymer and the first pore-forming agent in the step (1) is as follows: (10-30): (0.1-7): (8-30): (5-15); the mass ratio of the porous graphite material, the conductive agent, the polymer and the second pore-forming agent in the step (a) is as follows: (10-30): (0.1-7): (8-30): (5-15);
the average particle size D50 of the porous graphite material is 3-15 mu m, and the specific surface area of the porous graphite material is 1.0-2.5 m2/g。
2. The preparation method of the porous composite anode material for the lithium ion battery according to claim 1, wherein the porous graphite material is one or more than two composite materials of artificial graphite, natural graphite and mesocarbon microbeads with a porous structure.
3. The preparation method of the porous composite anode material for the lithium ion battery according to claim 1, wherein the preparation method of the porous graphite material comprises the following steps: soaking one or more than two composite materials of artificial graphite, natural graphite and mesocarbon microbeads in an alkaline aqueous solution for 5min to 48h at the soaking temperature of 20 ℃ to 60 ℃, then carrying out heat treatment for 0.5h to 48h at the temperature of 500 ℃ to 1200 ℃ under the protection of inert gas, washing with water and drying to obtain the composite material.
4. The preparation method of the porous composite anode material of the lithium ion battery according to claim 1, wherein the first pore-forming agent is an organic pore-forming agent; the second pore-forming agent is an oxide pore-forming agent; wherein said
The organic pore-forming agent is one of polystyrene, polyvinyl alcohol, polyethylene, polyvinyl acetate and polymethyl methacrylate; the oxide pore-forming agent is one of silicon dioxide, titanium dioxide, zinc oxide and copper oxide.
5. The preparation method of the porous composite anode material for the lithium ion battery according to claim 1, wherein the conductive agent is one or more of conductive carbon black, carbon nanotubes, nitrogen-doped carbon nanotubes, graphene, nitrogen-doped graphene and carbon fibers.
6. The preparation method of the porous composite anode material for the lithium ion battery according to claim 1, wherein the polymer is one or more of polyacrylonitrile, polyaniline, polypyrrole and polyimide.
7. The preparation method of the porous composite anode material for the lithium ion battery according to claim 1, wherein the electrospinning process parameters are as follows: the voltage is 5-20 kV, the speed of the electric spinning is 10-20 mu L/min, and the distance between the electrodes is 15-20 cm.
8. A porous composite anode material prepared by the preparation method of claim 1.
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