CN114497506A - Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof - Google Patents
Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The embodiment of the invention discloses a hard carbon-inorganic lithium salt composite electrode material which has a core-shell structure, wherein a core is phosphorus-doped hard carbon, a shell is an inorganic lithium salt layer, and the mass percentage of the shell is 1-10% based on the total weight of the composite material. The composite material is prepared by preparing a porous hard carbon material, depositing phosphorus trichloride in pores and on the surface of the porous hard carbon material to obtain a phosphorus-doped hard carbon core, and circularly depositing inorganic lithium salt on the surface of the core by an atomic vapor deposition method. The hard carbon-inorganic lithium salt electrode composite material can be used as a battery cathode material, the inner core of the composite material is doped with phosphorus, the doping is uniform, the consistency is good, the material is endowed with higher specific capacity, and the shell is internally provided with an ordered cyclic deposition layer of inorganic lithium salt, so that the first charge-discharge efficiency, the rate capability and the cycle performance of the material are greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a hard carbon-inorganic lithium salt composite electrode material and a preparation method thereof.
Background
The hard carbon is non-graphitizable amorphous carbon, has large interlayer spacing and good rapid charge and discharge performance, and particularly has excellent low-temperature charge and discharge performance. At present, hard carbon is mainly prepared from high molecular polymer materials, such as coconut shells, starch, resin and the like, and the high molecular polymer generates air holes in the pyrolysis process, so that the specific surface area of the hard carbon is higher, moisture and oxygen are easy to absorb, side reactions are more, and the first coulombic efficiency is lower.
In addition, the effective specific capacity of the hard carbon material is relatively low (about 300 mAh/g), and the electronic conductivity of the hard carbon material is deviated (one order of magnitude lower than that of graphite) due to the porous structure. For example, the specific capacity of the phosphorus doped material is improved, but the impedance of different phosphorus source materials is different, so that the specific capacity of the materials is improved in different amplitudes; if amorphous carbon coating is performed, the side reaction of the material can be reduced, and the first efficiency can be improved, but the specific capacity and the dynamic performance of the material can be reduced.
Therefore, for the hard carbon electrode material, various factors influence the performance of the hard carbon electrode material, and the obtained composite electrode material with better comprehensive performance is the direction of effort required in the prior art.
Disclosure of Invention
In view of the above disadvantages, the invention provides a hard carbon-inorganic lithium salt composite electrode material, which is a composite material with better comprehensive performance obtained by constructing a specific material structure and selecting appropriate raw materials.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the technical purpose of the first aspect of the invention is to provide a hard carbon-inorganic lithium salt electrode composite material, which has a core-shell structure, wherein the core is phosphorus-doped hard carbon, the shell is an inorganic lithium salt layer, and the mass percentage of the shell is 1-10% based on the total weight of the composite material.
Further, the inorganic lithium salt layer is an ordered cyclic deposition layer of inorganic lithium salt, and the number of deposition layers is 10-200, preferably 50-120.
Further, in one embodiment of the invention, the mass ratio of the hard carbon to the phosphorus compound in the core is 95-99: 1-5, and the phosphorus compound is phosphorus trichloride.
Further, in one of the embodiments of the present invention, the inorganic lithium salt is selected from at least one of lithium zirconate, lithium niobate, lithium titanate, and lithium silicate.
Further, in one embodiment of the present invention, the hard carbon-inorganic lithium salt electrode composite has a particle size of 2to 10 μm.
The technical purpose of the second aspect of the invention is to provide a preparation method of a hard carbon-inorganic lithium salt electrode composite material, which comprises the following steps:
preparation of the inner core: mixing and stirring the hard carbon precursor and an alkali solution for reaction, centrifuging, drying and carbonizing a product, and grinding and crushing to obtain a porous hard carbon material;
phosphorus doping: introducing phosphorus trichloride liquid into the porous hard carbon material, heating to gasify the phosphorus trichloride, and continuously introducing the phosphorus trichloride to deposit the phosphorus trichloride in the pores and on the surface of the porous hard carbon material to obtain a phosphorus-doped hard carbon core;
preparing the shell: and (3) circularly depositing inorganic lithium salt on the surface of the phosphorus-doped hard carbon core by adopting an atomic vapor deposition method to obtain the hard carbon-inorganic lithium salt electrode composite material.
Further, the hard carbon precursor is selected from at least one of phenolic resin, furfural resin, epoxy resin, glucose, sucrose, coconut shell, cyclodextrin, starch and styrene-butadiene rubber.
Further, the alkali solution is sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or ammonia hydroxide solution, the mass concentration of alkali in the alkali solution is 1-10 wt%, and the mass ratio of the hard carbon precursor to the alkali solution is 100: 1-10.
Further, the stirring reaction time of the hard carbon precursor and the alkali solution is 0.5-10 hours.
Further, the carbonization is carried out for 1-6h at the temperature of 600-1000 ℃ under the inert atmosphere; as a more specific implementation mode, the temperature is raised to 600-1000 ℃ at the speed of 1-10 ℃/min, and the temperature is naturally reduced to the room temperature after heat preservation and carbonization.
Further, the phosphorus doping process is performed in a tube furnace.
Further, heating to 100-200 ℃ in the phosphorus doping process to gasify the phosphorus chloride, and continuously introducing the phosphorus chloride for 1-6 h.
Further, the temperature of the atomic vapor deposition method is 150 to 250 ℃, and the pressure is 0.1to 0.5 Torr.
Further, as a more specific embodiment, the atomic vapor deposition method is operated as follows: placing the inner core of the phosphorus-doped hard carbon into a reaction cabin, vacuumizing the cabin to the pressure of 0.1-0.5 Torr, heating to 150-250 ℃, introducing inorganic lithium salt into the reaction cabin, and performing cyclic deposition on the outer surface of the inner core of the phosphorus-doped hard carbon, wherein the set program of the cyclic deposition is as follows: firstly, introducing inorganic lithium salt; blowing nitrogen; introducing an oxygen source; fourthly, nitrogen purging; introducing water; sixthly, purging by nitrogen; and sixthly, circulating for 10-200 circles, preferably 80-120 circles, forming an inorganic lithium salt deposition layer with uniform thickness on the surface of the phosphorus-doped hard carbon inner core layer by layer, and cooling to room temperature after completing the circulating deposition.
The technical purpose of the third aspect of the invention is to provide the application of the hard carbon-inorganic lithium salt electrode composite material as a battery negative electrode material.
The hard carbon-inorganic lithium salt electrode composite material has the advantages that the inner core is doped with phosphorus, the doping is uniform, the consistency is good, the material is endowed with higher specific capacity, the shell is internally provided with the ordered cyclic deposition layer of the inorganic lithium salt, and the first charge-discharge efficiency, the rate capability and the cycle performance of the material are greatly improved.
The embodiment of the invention has the following beneficial effects:
(1) the inner core of the hard carbon-inorganic lithium salt electrode composite material is formed by doping a phosphorus compound in a porous hard carbon precursor through a gas phase method, and forming the inner core with uniform doping and good consistency through proper phosphorus compound selection and a phosphorus doping mode, so that the specific capacity of the material is improved;
(2) according to the invention, lithium salt is deposited on the surface of the inner core by an atomic vapor deposition method to form an ordered cycle deposition layer of inorganic lithium salt, which is beneficial to providing sufficient lithium ions for the charge and discharge process by the lithium salt, so that the rate capability and the cycle capability of the composite material are improved, and meanwhile, the lithium salt is coated on the surface of the material to reduce the side reaction of the material and improve the first charge and discharge efficiency of the material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
fig. 1 is an SEM image of a hard carbon-inorganic lithium salt electrode composite prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Hard carbon-inorganic lithium salt electrode composites were prepared in examples 1-3:
example 1
S1, preparing an inner core:
mixing 100g of phenolic resin with 100mL of 5 wt% potassium hydroxide aqueous solution, continuously stirring for 2 hours, centrifuging and drying the product, then heating to 800 ℃ at the speed of 5 ℃/min under the inert atmosphere of argon, preserving the temperature for 3 hours, naturally cooling to room temperature, and grinding and crushing to obtain the porous hard carbon material.
S2, phosphorus doping:
and (3) transferring 100g of the porous hard carbon material prepared in the step S1 into a tubular furnace, introducing phosphorus trichloride liquid, heating to 150 ℃, gasifying the phosphorus trichloride material, and continuously introducing the phosphorus trichloride liquid for 3 hours at a flow rate of 10mL/min to deposit phosphorus trichloride in pores and on the surface of the porous hard carbon material to obtain the phosphorus-doped hard carbon inner core.
S3, preparing the shell:
placing the phosphorus-doped hard carbon core obtained in the step S2 in a reaction cabin, vacuumizing the cabin to the pressure of 0.2Torr, heating to 200 ℃, and introducing lithium zirconate into the reaction cabin for cyclic deposition, wherein the cyclic deposition is set by the following program: charging lithium zirconate for 10 seconds; blowing nitrogen for 60 seconds; introducing oxygen source for 10 seconds; fourthly, nitrogen purging is carried out for 10 seconds; introducing water for 1 second; sixthly, purging by nitrogen for 60 seconds; step one, circulation is carried out for 50 circles; and forming a lithium zirconate deposition layer with uniform thickness on the surface of the phosphorus-doped hard carbon core layer by layer, and cooling to room temperature after completing cyclic deposition to obtain the hard carbon-inorganic lithium salt electrode composite material.
Through material balance calculation, the mass percentage of the inorganic lithium salt layer shell is 5 percent based on the total weight of the composite material; the phosphorus trichloride accounts for 3 percent of the total weight of the inner core.
Example 2
S1, preparing an inner core:
mixing 100g of furfural resin with 100mL of 1 wt% potassium hydroxide aqueous solution, continuously stirring for 0.5 hour, centrifuging and drying the product, then heating to 600 ℃ at the speed of 1 ℃/min under the inert atmosphere of argon, preserving the temperature for 6 hours, naturally cooling to room temperature, grinding and crushing to obtain the porous hard carbon material.
S2, phosphorus doping:
and (3) transferring 100g of the porous hard carbon material prepared in the step S1 into a tubular furnace, introducing phosphorus trichloride liquid, heating to 100 ℃, gasifying the phosphorus trichloride material, and continuously introducing the phosphorus trichloride liquid for 6 hours at a flow rate of 10mL/min to deposit phosphorus trichloride in pores and on the surface of the porous hard carbon material to obtain the phosphorus-doped hard carbon inner core.
S3, preparing a shell:
placing the phosphorus-doped hard carbon core obtained in the step S2 in a reaction chamber, vacuumizing the chamber to the pressure of 0.1Torr, heating to 150 ℃, and introducing lithium niobate into the reaction chamber for cyclic deposition, wherein the cyclic deposition is set by the following program: charging lithium niobate for 1 second; blowing nitrogen for 60 seconds; introducing oxygen source for 5 seconds; fourthly, nitrogen purging is carried out for 5 seconds; introducing water for 0.05 second; sixthly, purging the nitrogen for 50 seconds; step I, circulation is carried out for 10 circles; and forming a lithium niobate deposition layer with uniform thickness on the surface of the phosphorus-doped hard carbon core layer by layer, and cooling to room temperature after completing the cyclic deposition to obtain the hard carbon-inorganic lithium salt electrode composite material.
Through material balance calculation, the mass percentage of the inorganic lithium salt layer shell is 1 percent based on the total weight of the composite material; the phosphorus trichloride accounts for 5 percent of the total weight of the inner core.
Example 3
S1, preparing an inner core:
mixing 100g of epoxy resin with 100mL of 10 wt% potassium hydroxide aqueous solution, continuously stirring for 10 hours, centrifuging and drying the product, then heating to 1000 ℃ at the speed of 10 ℃/min under the inert atmosphere of argon, preserving the temperature for 1 hour, naturally cooling to room temperature, and grinding and crushing to obtain the porous hard carbon material.
S2, phosphorus doping:
and (3) transferring 100g of the porous hard carbon material prepared in the step S1 into a tubular furnace, introducing phosphorus trichloride liquid, heating to 200 ℃, gasifying the phosphorus trichloride material, and continuously introducing the phosphorus trichloride liquid for 1h at the flow rate of 10mL/min to deposit phosphorus trichloride in the pores and the surface of the porous hard carbon material to obtain the phosphorus-doped hard carbon inner core.
S3, preparing the shell:
placing the phosphorus-doped hard carbon core obtained in the step S2 in a reaction cabin, vacuumizing the cabin to the pressure of 0.5Torr, heating to 250 ℃, introducing lithium titanate into the reaction cabin for cyclic deposition, wherein the cyclic deposition is set by the following program: charging lithium titanate for 1 second; blowing nitrogen for 60 seconds; introducing oxygen source for 5 seconds; fourthly, nitrogen purging is carried out for 5 seconds; introducing water for 0.05 second; sixthly, purging the nitrogen for 50 seconds; step I, circulation is carried out for 200 circles; and forming a lithium titanate deposition layer with uniform thickness on the surface of the phosphorus-doped hard carbon core layer by layer, and cooling to room temperature after completing cyclic deposition to obtain the hard carbon-inorganic lithium salt electrode composite material.
Through material balance calculation, the mass percentage of the inorganic lithium salt layer shell is 10 percent based on the total weight of the composite material; the phosphorus trichloride accounts for 1 percent of the total weight of the inner core.
Comparative example 1
Crushing and drying 100g of phenolic resin, heating to 800 ℃ at a speed of 5 ℃/min under an inert atmosphere of argon, preserving heat for 3h, naturally cooling to room temperature, and grinding and crushing to obtain a hard carbon precursor material; and then uniformly mixing 100g of hard carbon precursor material and 10g of petroleum asphalt, grinding, heating to 200 ℃ in an argon atmosphere, preserving heat for 1h, then heating to 800 ℃ and preserving heat for 3h, spontaneously cooling to room temperature, crushing and grading to obtain the hard carbon composite material.
Comparative example 2
A composite material was obtained by following the same procedure as in example 1, except that the phosphorus source in S2 was replaced with phosphoric acid.
Comparative example 3
S1, S2 are the same as in example 1;
s3, preparing the shell:
and (3) uniformly mixing the phosphorus-doped hard carbon core obtained in the step (S2), 5g of lithium zirconate and 2g of petroleum asphalt, grinding, heating to 200 ℃ in an argon atmosphere, keeping the temperature for 1h, then heating to 800 ℃ and keeping the temperature for 3h, spontaneously combusting and cooling to room temperature, crushing and grading to obtain the composite material.
And (3) performance determination:
(1) topography testing
SEM test was performed on the hard carbon-inorganic lithium salt electrode composite in example 1, and the test results are shown in fig. 1. As shown in FIG. 1, the composite material is granular, has uniform size distribution, and has a particle size of 4-8 μm.
(2) Physicochemical Properties and button cell test
The composite materials prepared in examples 1to 3 and comparative examples 1to 3 were subjected to particle size, true density, tap density, specific surface area, ash content and specific capacity thereof. The test method comprises the following steps: GBT-245332019 graphite cathode material for lithium ion battery
The composite materials in examples 1-3 and comparative examples 1-3 are used as negative electrode materials of lithium ion batteries to assemble button batteries.
The preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into a lithium ion battery negative electrode material, stirring and pulping, coating the mixture on copper foil, and drying and rolling to prepare a negative electrode plate; the binder used was LA132, the conductive agent was SP, the solvent was redistilled water, and the negative electrode materials were the composite materials prepared in examples and comparative examples, respectively, according to the negative electrode materials: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220mL, preparing a negative pole piece; LiPF in electrolyte6As electrolyte, a mixture of EC and DEC in a volume ratio of 1:1 isA solvent with electrolyte concentration of 1.3 mol/L; the metal lithium sheet is a counter electrode, and the diaphragm is a Polyethylene (PE) film. Button cell assembly was performed in an argon-filled glove box. The electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.00V-2.0V, the charging and discharging speed is 0.1C, and the multiplying power (5C, 0.1C) and the cycle performance (0.5C/0.5C, 100 times) of the button cell are tested at the same time.
The test results are shown in table 1.
TABLE 1
As can be seen from table 1, the composite materials prepared in examples 1to 3 have high specific capacity and first efficiency, which is because the core in the material is a phosphorus-doped porous hard carbon structure, which improves the lithium storage active sites of the material, improves the specific capacity of the material, and at the same time, the surface of the material is coated with an ordered cyclic lithium salt deposit layer, thereby reducing the side reactions on the surface of the material, improving the first efficiency and the kinetic performance thereof, and improving the cycle and the rate capability thereof.
(3) Testing the soft package battery:
the composite materials of examples 1to 3 and comparative examples 1to 3 were used as negative electrode materials, and a ternary material (LiNi) was used1/3Co1/ 3Mn1/3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/l) is electrolyte, and the celegard2400 is a diaphragm to prepare the 2Ah soft package battery.
Testing the cycle performance: the charging and discharging current is 5C/5C, the voltage range is 2.5-4.2V, and the cycle times are 200 times.
Testing rate performance: the pouch cells were tested for constant current ratio at 2C charging conditions.
The test results are shown in table 2.
TABLE 2
As can be seen from Table 2, the cycle performance of the lithium ion battery prepared by using the composite negative electrode materials obtained in examples 1-3 is obviously superior to that of the comparative example in each stage. Experimental results show that the lithium salt deposition layer in the shell prepared by the atomic vapor deposition method has the advantages of high density, stable structure, high conductivity and the like, improves the diffusion channel of lithium ions, reduces the diffusion resistance of the lithium ions, improves the conductivity of the material, and has better cycle performance and constant current ratio.
Claims (10)
1. The hard carbon-inorganic lithium salt electrode composite material is characterized by having a core-shell structure, wherein a core is phosphorus-doped hard carbon, a shell is an inorganic lithium salt layer, and the shell accounts for 1-10% by mass of the total weight of the composite material.
2. The hard carbon-inorganic lithium salt electrode composite material according to claim 1, wherein the inorganic lithium salt layer is an ordered cyclic deposition layer of inorganic lithium salt, and the number of deposition layers is 10 to 200.
3. The hard carbon-inorganic lithium salt electrode composite material as claimed in claim 1, wherein the mass ratio of the hard carbon to the phosphorus compound in the core is 95-99: 1-5, and the phosphorus compound is phosphorus trichloride.
4. The hard carbon-inorganic lithium salt electrode composite of claim 1, wherein the inorganic lithium salt is selected from at least one of lithium zirconate, lithium niobate, lithium titanate, and lithium silicate.
5. The hard carbon-inorganic lithium salt electrode composite according to claim 1, wherein the particle size of the composite is 2to 10 μm.
6. A preparation method of a hard carbon-inorganic lithium salt electrode composite material comprises the following steps:
preparation of an inner core: mixing and stirring the hard carbon precursor and an alkali solution for reaction, centrifuging, drying and carbonizing a product, and grinding and crushing to obtain a porous hard carbon material;
phosphorus doping: introducing phosphorus trichloride liquid into the porous hard carbon material, heating to gasify the phosphorus trichloride, and continuously introducing the phosphorus trichloride to deposit the phosphorus trichloride in the pores and on the surface of the porous hard carbon material to obtain a phosphorus-doped hard carbon core;
preparing the shell: and (3) circularly depositing inorganic lithium salt on the surface of the phosphorus-doped hard carbon core by adopting an atomic vapor deposition method to obtain the hard carbon-inorganic lithium salt electrode composite material.
7. The method according to claim 6, wherein the hard carbon precursor is at least one selected from the group consisting of phenolic resin, furfural resin, epoxy resin, glucose, sucrose, coconut shell, cyclodextrin, starch, and styrene-butadiene rubber.
8. The method as claimed in claim 6, wherein the phosphorus is gasified by heating to 100-200 ℃ during the phosphorus doping process, and the phosphorus chloride is continuously introduced for 1-6 hours.
9. The method of claim 6, wherein the temperature of the atomic vapor deposition method is 150 to 250 ℃ and the pressure is 0.1to 0.5 Torr.
10. Use of the hard carbon-inorganic lithium salt electrode composite of claim 1 or prepared by the method of claim 6 as a battery negative electrode material.
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