CN112687874B - High-stability lithium battery negative electrode material and application thereof - Google Patents
High-stability lithium battery negative electrode material and application thereof Download PDFInfo
- Publication number
- CN112687874B CN112687874B CN202011581360.7A CN202011581360A CN112687874B CN 112687874 B CN112687874 B CN 112687874B CN 202011581360 A CN202011581360 A CN 202011581360A CN 112687874 B CN112687874 B CN 112687874B
- Authority
- CN
- China
- Prior art keywords
- parts
- lithium battery
- negative electrode
- stability
- porous graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-stability lithium battery negative electrode material, and relates to the technical field of lithium batteries. The feed comprises the following raw materials in parts by weight: 20-30 parts of modified porous graphene, 20-30 parts of modified graphite, 20-30 parts of mesocarbon microbeads, 20-30 parts of lithium titanate, 5-10 parts of conductive agent and 5-10 parts of adhesive. The high-stability lithium battery cathode material provided by the invention adopts the specially-made modified porous graphene and modified graphite, and adopts the heat treatment of borane tert-butylamine and the ion exchange resin for exchanging cobalt ions to obtain the modified porous graphene, so that the modified porous graphene has a unique and stable three-dimensional structure; the mesocarbon microbeads can effectively control the aggravation of the negative polarization, finally obtain the high-capacity-density and long-life high-stability lithium battery negative material, and the high-capacity-density and long-life high-stability lithium battery negative material can still maintain good capacitance under the conditions of high temperature and low temperature, and the capacity retention rate R after the lithium battery is cycled for 2000 times at high temperature is higher than 80%.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a high-stability lithium battery negative electrode material and application thereof.
Background
As an environment-friendly high-energy-density secondary power source, a lithium ion battery has been widely used in small portable devices such as notebook computers and mobile phones, and compared with lead-acid batteries, nickel-cadmium batteries and nickel-hydrogen batteries, the lithium ion battery has the advantages of high energy density, long cycle life, small self-discharge, no memory effect, small environmental pollution and the like. With the continuous progress of science and technology, people put more and higher requirements on the performance of batteries: the miniaturization and personalization of electronic devices require batteries with smaller volumes and higher specific energy output; batteries required by aerospace energy have cycle life, better low-temperature charge and discharge performance and higher safety performance electric vehicles need batteries with high capacity, low cost, high stability and safety performance.
The current commercial lithium ion battery is made of LiCoO as the anode material 2 And the capacity limitation of the negative electrode material graphite carbon, in addition, the lithium battery is used in a high-temperature environment, the electrode polarization aggravation in the charging process is the main reason of rapid attenuation of the battery capacity at high temperature, and the charge transmission resistance is increased under the high-temperature condition, and the electrode is deformed due to the generation of a large amount of gas, so that the discharge capacity is further attenuated. The lithium ion battery still has the problems of poor cycle life, low energy density, poor rate capability and the like.
Therefore, how to provide a high-stability lithium battery anode material with high capacity density and long service life is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a high-stability lithium battery cathode material, which adopts specially-made modified porous graphene and modified graphite, and adopts heat-treated borane tert-butylamine and ion exchange resin for exchanging cobalt ions to obtain the modified porous graphene, and the modified porous graphene has a unique and stable three-dimensional structure, and is beneficial to storage and electron transmission of force ions; the nano-grade tin powder is adopted, so that the volume effect generated during charging and discharging due to larger particle size is avoided, the stability of a cathode material system is ensured, and the cathode material is subjected to composite coating treatment with graphite to improve the capacitance of the cathode material; the polarization of the negative electrode can be effectively controlled by adopting the mesocarbon microbeads to circulate under the high-temperature condition, so that the improvement of high-temperature circulation is realized, the volume expansion of the negative electrode with small particle size is not obvious in the charging and discharging processes, and finally the high-stability lithium battery negative electrode material with high capacity density and long service life is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-stability lithium battery negative electrode material comprises the following raw materials in parts by weight: 20-30 parts of modified porous graphene, 20-30 parts of modified graphite, 20-30 parts of mesocarbon microbeads, 20-30 parts of lithium titanate, 5-10 parts of a conductive agent and 5-10 parts of an adhesive.
The technical effect of adopting the technical scheme is as follows: the polarization of the negative electrode can be effectively controlled by adopting the mesocarbon microbeads to be circulated under the high-temperature condition, so that the high-temperature circulation is improved, the volume expansion of the negative electrode with small particle size is not obvious in the charging and discharging process, the tap density can reflect the morphology and the particle size distribution of the material, the volume energy density of the battery is too low due to too small tap density, the area of the formed SEI film is small due to the material with small specific surface area, the consumed lithium ions are few, the irreversible capacity is few, and the gas generation is also few.
Preferably, the modified porous graphene is prepared by the following method: sequentially carrying out acid washing and alkali washing on cation exchange resin, adding a cobalt salt solution with the concentration of 0.25-0.30M, stirring and reacting for 8-15h, cleaning and drying to obtain resin containing cobalt ions, adding an ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 8-15h, heating to remove ethanol, placing in a high-temperature tubular furnace for high-temperature sintering, and drying after post-treatment to obtain the modified porous graphene.
The technical effect of adopting the technical scheme is as follows: the modified porous graphene is obtained by adopting heat treatment of borane tert-butylamine and ion exchange resin for exchanging cobalt ions, has a unique and stable three-dimensional structure, is beneficial to storage and electron transmission of force ions, and has stable and excellent electrochemical performance due to the fact that the lithium ion active sites are increased and the conductivity is enhanced due to the doping of boron and nitrogen elements.
Preferably, the dosage ratio of the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide is as follows: (20-30) g: (200-300) mL: (10-20) g: (80-100) g.
Preferably, the high-temperature sintering operation is: heating at 800-1200 deg.C for 2-3h in nitrogen atmosphere, and naturally cooling to room temperature.
Preferably, the modified graphite is prepared by the following method: adding nano tin powder into ethanol, performing ultrasonic dispersion, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, and performing spray drying to obtain the modified graphite.
The technical effect of adopting the technical scheme is as follows: the nano-grade tin powder is adopted, so that the volume effect generated during charging and discharging due to larger particle size is avoided, the stability of a cathode material system is ensured, and the cathode material is subjected to composite coating treatment with graphite to improve the capacitance of the cathode material; in addition, the modified graphite can reduce the interlamellar spacing of the material and improve the space utilization rate of the material by improving the compaction density and the tap density of the graphite material, thereby achieving the effect of reducing the internal resistance of the material and improving the charge-discharge performance and the cycle performance of the material at low temperature.
Preferably, the mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: (5-10): (4-8): (5-20): (0.1-1): (90-120).
Preferably, the inlet temperature of the spray drying is 150-220 ℃, the outlet temperature is 50-80 ℃, and the drying time is 0.5-2h.
Preferably, the conductive agent is a mixture of one or more of acetylene black, carbon fiber and conductive carbon black; the binder is one or a mixture of two of styrene-butadiene rubber and carboxymethyl cellulose.
The invention also provides a preparation method of the high-stability lithium battery cathode material, which comprises the following steps: the preparation method comprises the steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, a conductive agent and an adhesive in sequence according to parts by weight, uniformly mixing, adding into a ball mill for ball milling and drying, wherein the rotating speed of a ball milling cylinder is 36-38r/min, calcining at the temperature of 850-900 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery cathode material.
The invention further provides an application of the preparation method of the high-stability lithium battery cathode material in preparation of a lithium battery, wherein the lithium battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, the lithium battery comprises a negative electrode current collector and a cathode material coated on the current collector, and the cathode material is the high-stability lithium battery cathode material.
According to the technical scheme, compared with the prior art, the high-stability lithium battery cathode material disclosed by the invention has the following beneficial effects:
(1) The high-stability lithium battery cathode material provided by the invention adopts specially-made modified porous graphene and modified graphite; the modified porous graphene is obtained by adopting heat treatment of borane tert-butylamine and ion exchange resin for exchanging cobalt ions, has a unique and stable three-dimensional structure, and is beneficial to storage and electron transmission of force ions; the nano-grade tin powder is adopted, so that the volume effect generated during charging and discharging due to larger particle size is avoided, the stability of a cathode material system is ensured, and the cathode material is subjected to composite coating treatment with graphite to improve the capacitance of the cathode material; the polarization of the negative electrode can be effectively controlled to be intensified by adopting the mesocarbon microbeads to circulate under the high-temperature condition, so that the improvement of high-temperature circulation is realized, the volume expansion of the negative electrode with small particle size is not obvious in the charging and discharging process, and finally the high-stability lithium battery negative electrode material with high capacity density and long service life is obtained.
(2) The high-stability lithium battery cathode material prepared by the invention is applied to the preparation of lithium batteries, can still keep good capacitance under the conditions of high temperature and low temperature, and has the capacity retention rate R higher than 80% after being cycled for 2000 times at high temperature.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
In the embodiment of the invention, the nano tin powder, the acetylene black, the carbon fiber, the cobalt acetate and the like are reagents which are conventionally purchased and used by a person skilled in the art, and the required equipment is commercially available production and processing equipment, so that the brand of the equipment is not required, and redundant description is not repeated.
The embodiment of the invention provides a high-stability lithium battery negative electrode material which comprises the following raw materials in parts by weight: 20-30 parts of modified porous graphene, 20-30 parts of modified graphite, 20-30 parts of mesocarbon microbeads, 20-30 parts of lithium titanate, 5-10 parts of a conductive agent and 5-10 parts of an adhesive.
In order to further optimize the technical scheme, the modified porous graphene is prepared by the following method: sequentially carrying out acid washing and alkali washing on cation exchange resin, adding a cobalt salt solution with the concentration of 0.25-0.30M, stirring and reacting for 8-15h, cleaning and drying to obtain resin containing cobalt ions, adding an ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 8-15h, heating to remove ethanol, placing in a high-temperature tube furnace, carrying out high-temperature sintering, and drying after post-treatment to obtain the modified porous graphene.
In order to further optimize the technical scheme, the dosage ratio of the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide is as follows: (20-30) g: (200-300) mL: (10-20) g: (80-100) g. Further, 0.3-0.5M hydrochloric acid solution is adopted for acid washing, and 0.3-0.5M sodium hydroxide solution is adopted for alkali washing; the cobalt salt is selected from cobalt acetate, cobalt carbonate, etc.
In order to further optimize the technical scheme, the operation of high-temperature sintering is as follows: heating at 800-1200 deg.C for 2-3h in nitrogen atmosphere, and naturally cooling to room temperature.
In order to further optimize the technical scheme, the modified graphite is prepared by the following method: adding nano tin powder into ethanol, performing ultrasonic dispersion for 0.5-1h at the frequency of 5kHz-50kHz, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, and performing spray drying to obtain the modified graphite.
In order to further optimize the technical scheme, the mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: (5-10): (4-8): (5-20): (0.1-1): (90-120).
In order to further optimize the technical scheme, the inlet temperature of spray drying is 150-220 ℃, the outlet temperature is 50-80 ℃, and the drying time is 0.5-2h.
In order to further optimize the technical scheme, the conductive agent is one or a mixture of acetylene black, carbon fiber and conductive carbon black; the binder is one or a mixture of two of styrene-butadiene rubber and carboxymethyl cellulose.
The invention also provides a preparation method of the high-stability lithium battery negative electrode material, which comprises the following steps of: the preparation method comprises the steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, a conductive agent and an adhesive in sequence according to the weight parts, uniformly mixing, adding into a ball mill for ball milling, drying, calcining at 850-900 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery cathode material.
Example 1
The embodiment provides a high-stability lithium battery negative electrode material which comprises the following raw materials in parts by weight: 30 parts of modified porous graphene, 30 parts of modified graphite, 20 parts of mesocarbon microbeads, 30 parts of lithium titanate, 5 parts of acetylene black and 10 parts of styrene butadiene rubber.
The modified porous graphene is prepared by the following method: sequentially carrying out acid washing on cation exchange resin by using 0.3M hydrochloric acid solution, carrying out alkali washing by using 0.3M sodium hydroxide solution, filtering to be neutral and drying, adding 0.25M cobalt acetate solution, stirring and reacting for 8h at the speed of 400r/min, cleaning and drying to obtain resin containing cobalt ions, adding ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 8h at the speed of 400r/min, heating to remove ethanol at 70 ℃, placing in a high-temperature tubular furnace, heating for 3h at the temperature of 800 ℃ in nitrogen atmosphere, naturally cooling to room temperature, respectively placing in 3M hydrochloric acid solution, stirring for 12h at the speed of 300r/min, removing impurities, and drying to obtain the modified porous graphene. The dosage ratio of the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide is as follows: 20g:200mL of: 10g:80g.
The modified graphite is prepared by the following method: adding nano tin powder into ethanol, ultrasonically dispersing for 1h at the frequency of 5kHz, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, spray drying at the inlet temperature of 220 ℃, the outlet temperature of 50 ℃ and the drying time of 0.5h, and spray drying to obtain the modified graphite. The mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: 5:4:20:1:90.
the embodiment also provides a preparation method of the high-stability lithium battery negative electrode material, which comprises the following steps: the preparation method comprises the steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, acetylene black and styrene butadiene rubber in sequence according to parts by weight, placing the materials into a vacuum stirrer, stirring at the speed of 20r/min for 90min at the stirring temperature of 20 ℃, uniformly mixing, adding the materials into a ball mill, carrying out ball milling and drying, calcining at the temperature of 900 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery cathode material.
Example 2
The embodiment provides a high-stability lithium battery negative electrode material which comprises the following raw materials in parts by weight: 20 parts of modified porous graphene, 20 parts of modified graphite, 30 parts of mesocarbon microbeads, 20 parts of lithium titanate, 10 parts of carbon fibers and 5 parts of carboxymethyl cellulose.
The modified porous graphene is prepared by the following method: sequentially carrying out acid washing on cation exchange resin by using 0.5M hydrochloric acid solution, carrying out alkali washing by using 0.5M sodium hydroxide solution, filtering to be neutral and drying, adding 0.25M cobalt carbonate solution, stirring and reacting for 15h at the speed of 400r/min, cleaning and drying to obtain resin containing cobalt ions, adding ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 15h at the speed of 400r/min, heating at 80 ℃ to remove ethanol, placing in a high-temperature tubular furnace, heating at 1200 ℃ for 2h in nitrogen atmosphere, naturally cooling to room temperature, respectively placing in 3M hydrochloric acid solution, stirring for 12h at the speed of 300r/min, removing impurities, and drying to obtain the modified porous graphene. The dosage ratio of the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide is as follows: 30g of: 300mL:20g:100g.
The modified graphite is prepared by the following method: adding nano tin powder into ethanol, ultrasonically dispersing for 0.5h at the frequency of 50kHz, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, spray drying at the inlet temperature of 150 ℃, the outlet temperature of 80 ℃ and the drying time of 2h, and spray drying to obtain the modified graphite. The mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: 10:8:5:0.1:120.
the embodiment also provides a preparation method of the high-stability lithium battery negative electrode material, which comprises the following steps: the preparation method comprises the following steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, carbon fibers and carboxymethyl cellulose in parts by weight in sequence, placing the materials into a vacuum stirrer, stirring at a speed of 40r/min for 60min at a stirring temperature of 50 ℃, uniformly mixing, adding the materials into a ball mill, carrying out ball milling and drying, calcining at a temperature of 850 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery cathode material.
Example 3
The embodiment provides a high-stability lithium battery negative electrode material which comprises the following raw materials in parts by weight: 25 parts of modified porous graphene, 25 parts of modified graphite, 25 parts of mesocarbon microbeads, 25 parts of lithium titanate, 8 parts of conductive carbon black and 8 parts of carboxymethyl cellulose.
The modified porous graphene is prepared by the following method: sequentially carrying out acid washing on cation exchange resin by using 0.4M hydrochloric acid solution, carrying out alkali washing by using 0.4M sodium hydroxide solution, filtering to be neutral and drying, adding 0.28M cobalt acetate solution, stirring and reacting for 12h at the speed of 400r/min, cleaning and drying to obtain resin containing cobalt ions, adding ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 12h at the speed of 400r/min, heating at 75 ℃ to remove ethanol, placing in a high-temperature tubular furnace, heating at 1000 ℃ in nitrogen atmosphere for 2.5h, naturally cooling to room temperature, respectively placing in 3M hydrochloric acid solution, stirring for 12h at the speed of 300r/min, removing impurities, and drying to obtain the modified porous graphene. The dosage ratio of the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide is as follows: 25g of: 250mL of: 15g:90g.
The modified graphite is prepared by the following method: adding nano tin powder into ethanol, ultrasonically dispersing for 0.8h at the frequency of 30kHz, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, spray drying at the inlet temperature of 200 ℃, the outlet temperature of 70 ℃ and the drying time of 1h, and spray drying to obtain the modified graphite. The mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: 8:6:15:0.5:100.
the embodiment also provides a preparation method of the high-stability lithium battery negative electrode material, which comprises the following steps: the preparation method comprises the following steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, conductive carbon black and carboxymethyl cellulose in parts by weight in sequence, placing the materials into a vacuum stirrer, stirring at the speed of 30r/min for 80min at the stirring temperature of 30 ℃, uniformly mixing, adding the materials into a ball mill, carrying out ball milling and drying, calcining at the temperature of 880 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery negative electrode material.
Comparative example 1
The raw materials and the amounts of the comparative example were substantially the same as those in example 3, except that: the modified porous graphene is replaced by common graphene.
Comparative example 2
The raw materials and the amounts of the comparative example were substantially the same as those in example 3, except that: the modified graphite is replaced by the common graphite.
Comparative example 3
The raw materials and the amounts of the comparative example were substantially the same as those in example 3, except that: no mesocarbon microbeads were added.
Comparative example 4
The raw materials and the amounts of the comparative example were substantially the same as those in example 3, except that: the modified porous graphene is replaced by common graphene, and the modified graphite is replaced by common graphite.
Electrochemical Performance test
In order to test the electrochemical performance of the high-stability lithium ion negative electrode material prepared by the method, a half-cell test method is used for testing, the negative electrode materials of the above examples 1-3 and comparative examples 1-4 are added with a proper amount of NMP (N-methyl pyrrolidone) to be mixed into slurry, the slurry is coated on a copper foil, and the slurry is dried for 8 hours at the temperature of 110 ℃ in vacuum to prepare a negative electrode sheet; the battery is assembled by using a metal lithium sheet as a counter electrode, an electrolyte of 1moJLLIPF6/EC + DEC + DMC =1 and a polypropylene microporous membrane as a diaphragm, and the performance of the battery is tested, wherein the test results are shown in Table 1.
Test method
(1) High temperature cycle performance: at 55 ℃, charging is carried out in a constant-current constant-voltage charging mode, the limiting current is 0.5C, the end voltage is 3.65V, the end current is 3.5A, discharging is carried out in a constant-current discharging mode, the discharging current is 1C, the cut-off voltage of discharging is 2.5V, the discharging is carried out for 2000 times in a circulating mode, and the capacity retention rate R of the initial discharging capacity C1, the discharging capacity C2 of 2000 times in the circulating mode and the capacity retention rate R after 2000 times in the circulating mode are respectively calculated.
(2) Low-temperature discharge performance: at 25 ℃, charging in a constant voltage charging mode, limiting current of 0.5C, final voltage of 3.65V and final current of 3.5A, discharging in a constant current discharging mode, discharging current of 1C, then charging in a constant voltage charging mode, limiting current of 0.5C, final voltage of 3.65V and final current of 3.5A, discharging at-20 ℃ in a constant current discharging mode, discharging current of 1C and discharging cut-off voltage of 2.0V, and respectively calculating 25 ℃ discharge capacity C3 and 20 ℃ discharge capacity C4. See table 1 specifically:
TABLE 1 electrochemical Properties of negative electrode materials for lithium batteries of examples 1 to 3 and comparative examples 1 to 4
As can be seen from the data in table 1, examples 1 to 3 of the present invention maintained good capacitance under high and low temperature conditions, and the capacity retention R after 2000 cycles at high temperature was higher than 80%, as compared to comparative examples 1 to 4.
In conclusion, the lithium battery cathode material prepared by the invention adopts the specially-made modified porous graphene and the modified graphite, and adopts the modified porous graphene obtained by heat treatment of the borane tert-butylamine and the ion exchange resin for exchanging cobalt ions, so that the modified porous graphene has a unique and stable three-dimensional structure and is beneficial to storage and electron transmission of force ions; the nano-grade tin powder is adopted, so that the volume effect generated during charging and discharging due to larger particle size is avoided, the stability of a cathode material system is ensured, and the cathode material is subjected to composite coating treatment with graphite to improve the capacitance of the cathode material; the polarization of the negative electrode can be effectively controlled by adopting the mesocarbon microbeads to circulate under the high-temperature condition, so that the improvement of high-temperature circulation is realized, the volume expansion of the negative electrode with small particle size is not obvious in the charging and discharging processes, and finally the high-stability lithium battery negative electrode material with high capacity density and long service life is obtained.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The high-stability lithium battery negative electrode material is characterized by comprising the following raw materials in parts by weight: 20-30 parts of modified porous graphene, 20-30 parts of modified graphite, 20-30 parts of mesocarbon microbeads, 20-30 parts of lithium titanate, 5-10 parts of conductive agent and 5-10 parts of adhesive;
the modified porous graphene is prepared by the following method: sequentially carrying out acid washing and alkali washing on cation exchange resin, adding a cobalt salt solution with the concentration of 0.25-0.30M, stirring and reacting for 8-15h, cleaning and drying to obtain resin containing cobalt ions, adding an ethanol solution of borane tert-butylamine and potassium hydroxide, stirring and reacting for 8-15h, heating to remove ethanol, placing in a high-temperature tubular furnace for high-temperature sintering, and drying after post-treatment to obtain modified porous graphene;
the modified graphite is prepared by the following method: adding nano tin powder into ethanol, performing ultrasonic dispersion, sequentially adding thiourea derivative, phenolic resin, hexamethylenetetramine and graphite, stirring and mixing to obtain uniform slurry, and performing spray drying to obtain modified graphite;
the mass ratio of the nano tin powder, the thiourea derivative, the phenolic resin, the hexamethylenetetramine and the graphite is as follows: (5-10): (4-8): (5-20): (0.1-1): (90-120);
the conductive agent is one or a mixture of acetylene black, carbon fiber and conductive carbon black; the adhesive is one or a mixture of two of styrene-butadiene rubber and carboxymethyl cellulose.
2. The high-stability negative electrode material for lithium batteries as claimed in claim 1, wherein the cation exchange resin, the cobalt salt solution, the borane tert-butylamine and the potassium hydroxide are used in a ratio of: (20-30) g: (200-300) mL: (10-20) g: (80-100) g.
3. The high-stability lithium battery negative electrode material as claimed in claim 1, wherein the high-temperature sintering operation is: heating at 800-1200 deg.C for 2-3h in nitrogen atmosphere, and naturally cooling to room temperature.
4. The high-stability lithium battery negative electrode material as claimed in claim 1, wherein the spray drying has an inlet temperature of 150-220 ℃, an outlet temperature of 50-80 ℃ and a drying time of 0.5-2h.
5. A method for preparing a negative electrode material for a high-stability lithium battery as defined in any one of claims 1 to 4, comprising the steps of: the preparation method comprises the steps of weighing modified porous graphene, modified graphite, mesocarbon microbeads, lithium titanate, a conductive agent and an adhesive in sequence according to the weight parts, uniformly mixing, adding into a ball mill for ball milling, drying, calcining at 850-900 ℃, cooling, crushing and sieving to obtain the high-stability lithium battery cathode material.
6. The use of the negative electrode material for a high-stability lithium battery as claimed in any one of claims 1 to 4, in the preparation of a lithium battery comprising a negative electrode current collector and the negative electrode material coated on the current collector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011581360.7A CN112687874B (en) | 2020-12-28 | 2020-12-28 | High-stability lithium battery negative electrode material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011581360.7A CN112687874B (en) | 2020-12-28 | 2020-12-28 | High-stability lithium battery negative electrode material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112687874A CN112687874A (en) | 2021-04-20 |
| CN112687874B true CN112687874B (en) | 2022-11-18 |
Family
ID=75453473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011581360.7A Active CN112687874B (en) | 2020-12-28 | 2020-12-28 | High-stability lithium battery negative electrode material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112687874B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683705A (en) * | 2012-04-24 | 2012-09-19 | 合肥国轩高科动力能源有限公司 | Lithium-titanate-coated modified graphite composite anode material, and preparation method and application thereof |
| CN105140521A (en) * | 2015-08-24 | 2015-12-09 | 深圳市斯诺实业发展有限公司 | Preparation method for negative electrode paste of lithium battery |
| CN108511752A (en) * | 2017-02-24 | 2018-09-07 | 宁德新能源科技有限公司 | Modified graphite cathode material and preparation method thereof and secondary cell |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208598B (en) * | 2011-05-12 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof |
| CN104064735B (en) * | 2013-03-18 | 2016-09-07 | 海洋王照明科技股份有限公司 | Lithium titanate-graphene-carbon nano tube composite material and its preparation method and application |
| US20160279619A1 (en) * | 2015-03-25 | 2016-09-29 | Brown University | Graphene-Supported NiPd Alloy Nanoparticles for Effective Catalysis of Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds |
| CN105140483A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method of modified lithium battery anode material |
| CN107240682B (en) * | 2017-05-27 | 2020-07-03 | 广东烛光新能源科技有限公司 | Lithium titanate negative electrode material and preparation method thereof |
| CN107180956B (en) * | 2017-05-27 | 2020-04-28 | 广东烛光新能源科技有限公司 | Lithium titanate negative electrode material and preparation method thereof |
| US11038195B2 (en) * | 2018-06-01 | 2021-06-15 | Global Graphene Group, Inc. | Multi-level graphene-protected anode active material particles for battery applications |
| CN109980197A (en) * | 2019-03-13 | 2019-07-05 | 湖南华慧新能源股份有限公司 | A kind of negative electrode material for lithium battery |
| CN111500001B (en) * | 2020-06-12 | 2022-04-12 | 南京工业大学 | Preparation method and application of carbon nanotube nano composite material |
-
2020
- 2020-12-28 CN CN202011581360.7A patent/CN112687874B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683705A (en) * | 2012-04-24 | 2012-09-19 | 合肥国轩高科动力能源有限公司 | Lithium-titanate-coated modified graphite composite anode material, and preparation method and application thereof |
| CN105140521A (en) * | 2015-08-24 | 2015-12-09 | 深圳市斯诺实业发展有限公司 | Preparation method for negative electrode paste of lithium battery |
| CN108511752A (en) * | 2017-02-24 | 2018-09-07 | 宁德新能源科技有限公司 | Modified graphite cathode material and preparation method thereof and secondary cell |
Non-Patent Citations (1)
| Title |
|---|
| 锂离子电池负极材料研究进展;李春晓;《关注》;20170905;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112687874A (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103199258B (en) | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery | |
| CN103280571B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN109103433B (en) | Nitrogen-doped carbon-coated lithium iron phosphate composite material and preparation method thereof | |
| CN106935830B (en) | lithium ion battery composite positive electrode material and preparation method and application thereof | |
| US20220077456A1 (en) | Core-shell nickel ferrite and preparation method thereof, nickel ferrite@c material and preparation method and application thereof | |
| CN102664247B (en) | Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating | |
| CN115566170B (en) | Preparation method of high-energy-density quick-charging lithium ion battery anode material | |
| CN114204027A (en) | Lithium ion battery positive pole piece, preparation method thereof and lithium ion battery | |
| CN111952670A (en) | Lithium ion battery with wide working temperature range | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| CN113690420B (en) | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof | |
| CN109802127B (en) | Preparation method of silver-doped ferroferric oxide nano composite material | |
| CN116885144B (en) | Silicon-carbon composite material for lithium battery cathode material and preparation method thereof | |
| CN117559013A (en) | Lithium supplementing agent composite material and preparation method and application thereof | |
| CN112687874B (en) | High-stability lithium battery negative electrode material and application thereof | |
| CN116454215A (en) | Preparation method and application of micron silicon composite anode material | |
| CN115172680A (en) | High-capacity high-rate lithium ion battery and preparation method thereof | |
| CN112751014A (en) | Aqueous energy storage battery based on layered vanadium oxide negative electrode | |
| CN111261857B (en) | FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN113725434B (en) | Nickel-based metal organic frame derived composite electrode and preparation method thereof | |
| CN111403724B (en) | Modified N, P co-doped lithium titanate negative electrode material and preparation method thereof | |
| CN115295781B (en) | Manganese-based positive electrode material and application thereof in lithium battery | |
| WO2020253285A1 (en) | Porous graphene lithium cobaltate composite material, preparation method therefor, and use thereof | |
| CN115799510A (en) | Graphene composite conductive agent and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A High Stability Negative Electrode Material for Lithium Batteries and Its Application Effective date of registration: 20230614 Granted publication date: 20221118 Pledgee: Postal Savings Bank of China Limited Hegang branch Pledgor: LUOBEI AOXING NEW MATERIALS CO.,LTD. Registration number: Y2023230000049 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |