CN114735690B - Preparation method of artificial graphite composite negative electrode material for lithium ion battery - Google Patents
Preparation method of artificial graphite composite negative electrode material for lithium ion battery Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a preparation method of an artificial graphite composite negative electrode material for a lithium ion battery, which comprises the following steps: feeding the graphite additive and the modified bismuth oxide into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished; and fifthly, carrying out heat treatment on the product obtained in the fourth step for 1 to 3 hours, protecting by using nitrogen, and finishing the heat treatment to obtain the artificial graphite composite negative electrode material. The artificial graphite composite negative electrode material is prepared by stirring and improving a graphite additive and modified bismuth oxide in a dispersion improved liquid and finally performing heat treatment, wherein the modified boron trioxide is adopted for improvement in thermal modification, and the graphite is doped with boron nonmetal elements to improve the state of the graphite and enhance the insertion amount of lithium ions; the specific capacity and the circulating effect of the product are improved by matching the modified bismuth oxide and the graphite additive.
Description
Technical Field
The invention relates to the technical field of lithium ion negative electrode materials, in particular to a preparation method of an artificial graphite composite negative electrode material for a lithium ion battery.
Background
Lithium ion battery: is a secondary battery (rechargeable battery) that operates by mainly relying on lithium ions moving between a positive electrode and a negative electrode. In the process of charging and discharging, li + is inserted and extracted back and forth between the two electrodes, wherein during charging, li + is extracted from the positive electrode and inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true when discharging; the main constituent materials of the lithium battery comprise electrolyte, isolating materials, anode and cathode materials and the like; the lithium battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like, wherein the positive electrode material accounts for more than 40% of the total cost of the lithium battery, and the performance of the positive electrode material directly influences various performance indexes of the lithium battery, so that the positive electrode material of the lithium battery occupies a core position in the lithium battery. The positive electrode (cathode) manganese dioxide is a main component and is used for generating chemical reactions of charge and discharge, and an additive component is used for improving the performance of the battery; the positive electrode material occupies a large proportion (the mass ratio of the positive electrode material to the negative electrode material is 3:1-4:1), because the performance of the positive electrode material directly influences the performance of the lithium battery, the cost directly determines the cost of the battery; the negative electrode (anode) metal lithium or alloy metal thereof is used as a negative electrode material, and the negative electrode material is coated on copper foil and on a negative electrode.
The conventional negative electrode material adopts graphite to coat polyaniline and other raw materials, enhances the lithium intercalation and separation function of the negative electrode material, can realize a quick charge function, but has poor stability, poor cycle performance and reduced capacity retention rate, and for example, chinese patent document CN113964311A discloses a graphite negative electrode material and a preparation method and application thereof, wherein the graphite negative electrode material is of a core-shell structure, an inner core of the core-shell structure is graphite, and the surface of the graphite is coated with a polytriphenylamine coating layer; based on the method, the invention further improves the method and realizes the harmonious enhancement of the product performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an artificial graphite composite negative electrode material for a lithium ion battery, so as to solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the invention provides a preparation method of an artificial graphite composite negative electrode material for a lithium ion battery, which comprises the following steps:
step one, adding a graphite additive: placing 25-35 parts of artificial graphite in a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive after the treatment is finished;
step two, preparing the dispersion improved liquid: adding 3-6 parts of bis (dioctyloxy pyrophosphate) ethylene titanate, 0.5-0.7 part of citric acid, 0.1-0.3 part of sodium persulfate aqueous solution and 0.1-0.2 part of lanthanum sulfate into 15-25 parts of deionized water, and fully stirring and mixing to obtain a dispersion modified liquid;
selecting raw materials: weighing 45-55 parts of graphite additive, 5-10 parts of modified bismuth oxide and 55-65 parts of dispersion modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
and fifthly, carrying out heat treatment on the product obtained in the fourth step for 1-3 h, adopting nitrogen for protection, and obtaining the artificial graphite composite negative electrode material after the treatment is finished.
Preferably, the power of the plasma treatment in the plasma chamber in the first step is 100-300W, and the treatment time is 5-10 min.
Preferably, the specific operation steps of the thermal modification treatment are as follows:
s01: the reaction temperature is firstly increased to 85-95 ℃ and preheated for 10-20 min;
s02: then adding modified boron trioxide accounting for 5-9% of the total amount of the S01 product, and fully stirring at constant temperature;
s03: heating to 155-165 ℃ at the speed of 1-3 ℃/s, keeping the temperature for 5-10 min, then heating to 275-285 ℃, continuing to react for 1-5 min, and finally cooling to room temperature in air.
Preferably, the modification method of the modified diboron trioxide is as follows: and (2) sending 5-10 parts of boron trioxide into 1-2 parts of phosphoric acid, 1-2 parts of oxalic acid, 9-11 parts of deionized water and 1-2 parts of silane coupling agent, stirring and mixing fully, and then washing and drying to obtain the boron trioxide.
The inventor of the invention finds that in the preparation of the graphite additive, the maximum charging multiplying power and the first charging specific capacity are obviously reduced and the capacity retention rate is also deteriorated after 100 cycles of circulation without adopting modified boron trioxide thermal modification treatment;
meanwhile, the boron trioxide in the modified boron trioxide is replaced by silicon dioxide, and although the optimization effect can be achieved, the improvement effect of the modified boron trioxide is not the most obvious as that of the boron trioxide.
Preferably, the silane coupling agent is KH570.
Preferably, the mass fraction of the sodium persulfate aqueous solution in the second step is 35-40%.
Preferably, the modification method of the modified bismuth oxide is as follows:
s11: 10-20 parts of bismuth trioxide is fed into 20-30 parts of phosphoric acid solution with the mass fraction of 30%, then 0.5-0.9 part of sodium dodecyl benzene sulfonate is added, and the mixture is uniformly dispersed to obtain first modification liquid;
s12: adding 1-5 parts of tartaric acid into 10-20 parts of ethanol, then adding 2-3 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: and (3) adding 5-10 parts of the second modification solution in the S12 into the first modification solution in the S11, then adding 1-3 parts of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain the modified bismuth oxide.
The inventor of the invention finds that the modified bismuth oxide can obviously improve the capacity retention rate of the product in 100 cycles, but the maximum charge rate is slightly influenced by the addition, but the influence is not very high, and meanwhile, the electrochemical performance of the product can be obviously enhanced by the matching of the modified bismuth oxide and the graphite additive;
preferably, the ultrasonic power in S13 is 550-650W, and the ultrasonic time is 15-25 min.
Preferably, the stirring temperature of the stirring dispersion treatment in the fourth step is 55-65 ℃, the stirring time is 15-25 min, and the stirring speed is 500-700 r/min.
The inventor of the invention finds that the dispersion modified liquid can improve the electrochemical performance of the product, and the dispersion modified liquid prepared by the invention has the best improvement effect and is not improved by other ways.
Preferably, the temperature of the heat treatment in the fifth step is 310-320 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the artificial graphite composite negative electrode material is prepared by stirring and improving a graphite additive and modified bismuth oxide in a dispersion improved liquid and finally performing heat treatment; the graphite additive is prepared by carrying out plasma treatment on artificial graphite and then carrying out thermal modification, so that on one hand, in order to improve the activity, open a lamellar layer and improve the contact effect of the graphite additive and the raw material of the modified bismuth oxide, the improvement effect of the modified bismuth oxide on the graphite additive is improved; in addition, the thermal modification is improved by adopting modified boron trioxide, the state of graphite is improved by doping boron nonmetal elements into the graphite, and the insertion amount of lithium ions is increased; the specific capacity and the circulation effect of the product are improved by matching the modified bismuth oxide and the graphite additive;
the dispersion modified liquid is prepared from bis (dioctyloxy pyrophosphate) ethylene titanate, citric acid, sodium persulfate aqueous solution and lanthanum sulfate, and can improve the compatibility of graphite additive and modified bismuth oxide interface, improve the auxiliary action of bismuth oxide modifier on the product, and thus enhance the electrochemical performance of the product in a coordinated manner.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, 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.
The preparation method of the artificial graphite composite negative electrode material for the lithium ion battery comprises the following steps:
step one, adding a graphite additive: placing 25-35 parts of artificial graphite in a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive after the treatment is finished;
step two, preparing the dispersion improved liquid: adding 3-6 parts of bis (dioctyloxy pyrophosphate) ethylene titanate, 0.5-0.7 part of citric acid, 0.1-0.3 part of sodium persulfate aqueous solution and 0.1-0.2 part of lanthanum sulfate into 15-25 parts of deionized water, and fully stirring and mixing to obtain a dispersion modified liquid;
selecting raw materials: weighing 45-55 parts of graphite additive, 5-10 parts of modified bismuth oxide and 55-65 parts of dispersion modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
and fifthly, carrying out heat treatment on the product obtained in the fourth step for 1-3 h, protecting by adopting nitrogen, and finishing the treatment to obtain the artificial graphite composite negative electrode material.
In the first step of this embodiment, the power of the plasma treatment in the plasma chamber is 100-300W, and the treatment time is 5-10 min.
The specific operation steps of the thermal modification treatment in this example are:
s01: the reaction temperature is firstly increased to 85-95 ℃ and preheated for 10-20 min;
s02: then adding modified boron trioxide accounting for 5-9% of the total amount of the S01 product, and fully stirring at constant temperature;
s03: heating to 155-165 ℃ at the speed of 1-3 ℃/s, keeping the temperature for 5-10 min, then heating to 275-285 ℃, continuing to react for 1-5 min, and finally cooling to room temperature in air.
The modification method of the modified diboron trioxide of the embodiment comprises the following steps: and (2) feeding 5-10 parts of diboron trioxide into 1-2 parts of phosphoric acid, 1-2 parts of oxalic acid, 9-11 parts of deionized water and 1-2 parts of silane coupling agent, stirring and mixing fully, and then washing and drying to obtain the diboron trioxide.
The silane coupling agent of this example was KH570.
In the second step of this example, the mass fraction of the aqueous sodium persulfate solution was 35 to 40%.
The modification method of the modified bismuth oxide of the embodiment comprises the following steps:
s11: sending 10-20 parts of bismuth trioxide into 20-30 parts of phosphoric acid solution, then adding 0.5-0.9 part of sodium dodecyl benzene sulfonate, and uniformly dispersing to obtain a first modified solution;
s12: adding 1-5 parts of tartaric acid into 10-20 parts of ethanol, then adding 2-3 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: and (3) adding 5-10 parts of the second modification solution in the S12 into the first modification solution in the S11, then adding 1-3 parts of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain the modified bismuth oxide.
In the embodiment, the ultrasonic power in S13 is 550 to 650W, and the ultrasonic time is 15 to 25min.
In the fourth step of this embodiment, the stirring temperature of the stirring dispersion treatment is 55-65 ℃, the stirring time is 15-25 min, and the stirring speed is 500-700 r/min.
The temperature of the heat treatment in the fifth step of this example is 310 to 320 ℃.
Example 1.
The preparation method of the artificial graphite composite negative electrode material for the lithium ion battery comprises the following steps:
step one, adding graphite: placing 25 parts of artificial graphite into a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive after the treatment is finished;
step two, preparing the dispersion improved liquid: adding 3 parts of bis (dioctyloxypyrophosphate) ethylene titanate, 0.5 part of citric acid, 0.1 part of sodium persulfate aqueous solution and 0.1 part of lanthanum sulfate into 15 parts of deionized water, and stirring and mixing fully to obtain a dispersion modified liquid;
selecting raw materials: weighing 45 parts of graphite additive, 5 parts of modified bismuth oxide and 55 parts of dispersion modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
and fifthly, carrying out heat treatment on the product obtained in the fourth step for 1h, protecting by adopting nitrogen, and finishing the treatment to obtain the artificial graphite composite negative electrode material.
In the first step of this embodiment, the processing power in the plasma chamber is 100W, and the processing time is 5min.
The specific operation steps of the thermal modification treatment in this example are:
s01: the reaction temperature is firstly increased to 85 ℃ and preheated for 10min;
s02: then adding modified boron trioxide accounting for 5 percent of the total amount of the product of the S01, and fully stirring at constant temperature;
s03: heating to 155 ℃ at the speed of 1 ℃/s, keeping the temperature for 5min, then heating to 275 ℃, continuing to react for 1min, and finally cooling to room temperature in air.
The modification method of the modified diboron trioxide of the embodiment comprises the following steps: and (2) feeding 5 parts of diboron trioxide into 1 part of phosphoric acid, 1 part of oxalic acid, 9 parts of deionized water and 1 part of silane coupling agent, stirring and mixing fully, and then washing and drying to obtain the diboron trioxide.
The silane coupling agent of this example was KH570.
The mass fraction of the aqueous sodium persulfate solution in the second step of this example was 35%.
The modification method of the modified bismuth oxide of the embodiment comprises the following steps:
s11: sending 10 parts of bismuth trioxide into 20 parts of phosphoric acid solution, then adding 0.5 part of sodium dodecyl benzene sulfonate, and uniformly dispersing to obtain a first modified solution;
s12: adding 1 part of tartaric acid into 10 parts of ethanol, then adding 2 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: and (3) adding 5 parts of the second modified solution in the S12 into the first modified solution in the S11, then adding 1 part of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain the modified bismuth oxide.
The ultrasonic power in S13 of this example is 550W, and the ultrasonic time is 15min.
In the fourth step of this example, the stirring temperature of the stirring dispersion treatment is 55 ℃, the stirring time is 15min, and the stirring speed is 500r/min.
The temperature of the heat treatment in the fifth step of this example was 310 ℃.
Example 2.
The preparation method of the artificial graphite composite negative electrode material for the lithium ion battery comprises the following steps:
step one, adding a graphite additive: placing 35 parts of artificial graphite into a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive after the treatment is finished;
step two, preparing the dispersion improved liquid: adding 6 parts of bis (dioctyloxypyrophosphate) ethylene titanate, 0.7 part of citric acid, 0.3 part of sodium persulfate aqueous solution and 0.2 part of lanthanum sulfate into 15-25 parts of deionized water, and stirring and mixing fully to obtain a dispersion modified liquid;
selecting raw materials: weighing 55 parts of graphite additive, 10 parts of modified bismuth oxide and 65 parts of dispersion modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
and fifthly, carrying out heat treatment on the product obtained in the fourth step for 3 hours, protecting by adopting nitrogen, and finishing the treatment to obtain the artificial graphite composite negative electrode material.
In the first step of this embodiment, the processing power in the plasma chamber is 300W, and the processing time is 10min.
The specific operation steps of the thermal modification treatment in this example are:
s01: the reaction temperature is firstly increased to 95 ℃ and preheated for 20min;
s02: then adding modified boron trioxide accounting for 9 percent of the total amount of the product of the S01, and fully stirring at constant temperature;
s03: heating to 165 ℃ at the speed of 3 ℃/s, keeping the temperature for 10min, then heating to 285 ℃, continuing to react for 5min, and finally cooling to room temperature in air.
The modification method of the modified diboron trioxide of the embodiment comprises the following steps: and (2) sending 10 parts of diboron trioxide into 2 parts of phosphoric acid, 2 parts of oxalic acid, 11 parts of deionized water and 2 parts of silane coupling agent, stirring and mixing fully, and then washing and drying to obtain the diboron trioxide.
The silane coupling agent of this example was KH570.
The mass fraction of the aqueous sodium persulfate solution in the second step of this example was 40%.
The modification method of the modified bismuth oxide of the embodiment comprises the following steps:
s11: feeding 20 parts of bismuth trioxide into 30 parts of phosphoric acid solution, adding 0.9 part of sodium dodecyl benzene sulfonate, and uniformly dispersing to obtain a first modified solution;
s12: adding 5 parts of tartaric acid into 20 parts of ethanol, then adding 3 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: and (3) adding 10 parts of the second modification solution in the S12 into the first modification solution in the S11, then adding 3 parts of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain the modified bismuth oxide.
The ultrasonic power in S13 of this example was 650, and the ultrasonic time was 25min.
In the fourth step of this example, the stirring temperature of the stirring dispersion treatment is 65 ℃, the stirring time is 25min, and the stirring speed is 700r/min.
The temperature of the heat treatment in the fifth step of this example was 320 ℃.
Example 3.
The preparation method of the artificial graphite composite negative electrode material for the lithium ion battery comprises the following steps:
step one, adding graphite: placing 30 parts of artificial graphite into a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive after the treatment is finished;
step two, preparing the dispersion improved liquid: adding 4.5 parts of bis (dioctyloxy pyrophosphate) ethylene titanate, 0.6 part of citric acid, 0.2 part of sodium persulfate aqueous solution and 0.15 part of lanthanum sulfate into 20 parts of deionized water, and stirring and mixing fully to obtain a dispersion modified liquid;
selecting raw materials: weighing 50 parts of graphite additive, 7.5 parts of modified bismuth oxide and 60 parts of dispersed modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
and fifthly, carrying out heat treatment on the product obtained in the fourth step for 2 hours, protecting by adopting nitrogen, and finishing the treatment to obtain the artificial graphite composite negative electrode material.
In the first step of this example, the processing power in the plasma chamber was 200W, and the processing time was 7.5min.
The specific operation steps of the thermal modification treatment in this example are:
s01: the reaction temperature is firstly increased to 90 ℃ and preheated for 15min;
s02: then adding modified boron trioxide accounting for 7 percent of the total amount of the product of the S01, and fully stirring at constant temperature;
s03: heating to 160 ℃ at the speed of 2 ℃/s, keeping the temperature for 7.5min, then heating to 280 ℃, continuing to react for 3min, and finally cooling to room temperature in air.
The modification method of the modified diboron trioxide of the embodiment comprises the following steps: and (2) sending 7.5 parts of diboron trioxide into 1.5 parts of phosphoric acid, 1.5 parts of oxalic acid, 10 parts of deionized water and 1.5 parts of silane coupling agent, stirring and mixing fully, and then washing and drying to obtain the diboron trioxide.
The silane coupling agent of this example was KH570.
The mass fraction of the aqueous sodium persulfate solution in the second step of this example was 37.5%.
The modification method of the modified bismuth oxide of the embodiment comprises the following steps:
s11: sending 15 parts of bismuth trioxide into 25 parts of phosphoric acid solution, then adding 0.7 part of sodium dodecyl benzene sulfonate, and uniformly dispersing to obtain a first modified solution;
s12: adding 3 parts of tartaric acid into 15 parts of ethanol, then adding 2.5 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: and (3) adding 7.5 parts of the second modification solution in the S12 into the first modification solution in the S11, then adding 2 parts of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain the modified bismuth oxide.
In the present embodiment, the ultrasonic power in S13 is 600, and the ultrasonic time is 20min.
In the fourth step of this example, the stirring temperature of the stirring dispersion treatment is 60 ℃, the stirring time is 20min, and the stirring speed is 600r/min.
The temperature of the heat treatment in the fifth step of this example was 315 ℃.
Comparative example 1.
Different from the embodiment 3, the specific operation steps of the heat modification treatment in the preparation of the graphite additive are different;
s01: the reaction temperature is firstly increased to 90 ℃ and preheated for 15min;
s01: heating to 160 ℃ at the speed of 2 ℃/s, keeping the temperature for 7.5min, then heating to 280 ℃, continuing to react for 3min, and finally cooling to room temperature in air.
Comparative example 2.
The difference from example 3 is that the boron trioxide in the modified boron trioxide is replaced by silica.
Comparative example 3.
In contrast to example 3, no modified bismuth oxide was added.
Comparative example 4.
Different from example 3 in the modification method of bismuth oxide;
s11: sending 15 parts of bismuth trioxide into 25 parts of 5% hydrochloric acid solution by mass, then adding 0.7 part of sodium alginate, and uniformly dispersing to obtain a first modified solution;
s12: adding 3 parts of sodium pyrophosphate into 15 parts of ethanol, then adding 2.5 parts of sodium lignosulphonate, and fully stirring to obtain a second modified solution;
s13: and (3) adding 7.5 parts of the first modification solution in the S12 into the first modification solution in the S11, then adding 2 parts of silicon dioxide, carrying out sufficient ultrasonic reaction, washing with water, and drying to obtain the modified bismuth oxide.
Comparative example 5.
The difference from example 3 is that bismuth oxide in the modified bismuth oxide was replaced with tin oxide.
Comparative example 6.
In contrast to example 3, no dispersion-modified liquor treatment was used.
Comparative example 7.
Different from the example 3 in the preparation method of the dispersion modified liquid;
adding 4.5 parts of silane coupling agent KH560, 0.6 part of ethylene glycol, 0.2 part of sodium alginate solution with the mass fraction of 5% and 0.15 part of cobalt sulfate into 20 parts of deionized water, and stirring and mixing fully to obtain the dispersion modified liquid.
The electrochemical properties of the products of examples 1-3 and comparative examples 1-7 were tested as follows:
as can be seen from comparative examples 1-2 and example 3, in the preparation of the graphite additive, modified diboron trioxide thermal modification treatment is not adopted, the maximum charging rate and the first charging specific capacity are obviously reduced, and the capacity retention rate is also deteriorated after 100 cycles;
meanwhile, the modified boron trioxide is replaced by silicon dioxide, which has an optimization effect but has the most obvious improvement effect compared with the boron trioxide adopted by the invention;
from comparative examples 3-5, it can be seen that the modified bismuth oxide can significantly improve the capacity retention rate of the product in 100 cycles, but the maximum charge rate is slightly influenced by the addition, but the influence is not very high, and meanwhile, the electrochemical performance of the product can be significantly enhanced by the combination of the modified bismuth oxide and the graphite additive;
it can be seen from comparative examples 6 to 7 that the dispersion-modified liquids can improve the electrochemical properties of the products, and the dispersion-modified liquids prepared according to the present invention are improved most effectively and in other ways, are not improved as much as the present invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. A preparation method of an artificial graphite composite negative electrode material for a lithium ion battery is characterized by comprising the following steps:
step one, adding graphite: placing 25-35 parts of artificial graphite in a plasma box for treatment, and then carrying out thermal modification treatment to obtain a graphite additive;
step two, preparing the dispersion improved liquid: adding 3~6 parts of bis (dioctyloxypyrophosphate) ethylene titanate, 0.5 to 0.7 part of citric acid, 0.1 to 0.3 part of sodium persulfate aqueous solution and 0.1 to 0.2 part of lanthanum sulfate into 15 to 25 parts of deionized water, and stirring and mixing fully to obtain a dispersion improved liquid;
selecting raw materials: weighing 45-55 parts of the graphite additive, 5-10 parts of modified bismuth oxide and 55-65 parts of dispersion modified liquid in the first step;
step four, feeding the graphite additive and the modified bismuth oxide in the step two into the dispersion modified liquid, stirring and dispersing, and washing and drying after the treatment is finished;
step five, carrying out heat treatment on the product obtained in the step four for 1 to 3 hours, and carrying out protection by adopting nitrogen gas to obtain an artificial graphite composite negative electrode material after the treatment is finished;
in the first step, the processing power in the plasma box is 100 to 300W, and the processing time is 5 to 10min;
the specific operation steps of the thermal modification treatment are as follows:
s01: heating the reaction temperature to 85 to 95 ℃ and preheating for 10 to 20min;
s02: then adding modified boron trioxide accounting for 5~9 percent of the total amount of the S01 product, and stirring fully at constant temperature;
s03: heating to 155-165 ℃ at the speed of 1~3 ℃/s, continuously preserving heat for 5-10min, then heating to 275-285 ℃, continuously reacting for 1-5min, and finally air-cooling to room temperature;
the modification method of the modified diboron trioxide comprises the following steps: feeding 5 to 10 parts of boron trioxide into 1~2 parts of phosphoric acid, 1~2 parts of oxalic acid, 9 to 11 parts of deionized water and 1~2 parts of silane coupling agent, stirring and mixing fully, then washing with water and drying to obtain boron trioxide; the modification method of the modified bismuth oxide comprises the following steps:
s11: sending 10-20 parts of bismuth trioxide into 20-30 parts of phosphoric acid solution with the mass fraction of 30%, then adding 0.5-0.9 part of sodium dodecyl benzene sulfonate, and uniformly dispersing to obtain a first modification solution;
s12: adding 1~5 parts of tartaric acid into 10-20 parts of ethanol, then adding 2~3 parts of chitosan, and fully stirring to obtain a second modified solution;
s13: adding 5-10 parts of the second modification solution in the S12 into the first modification solution in the S11, then adding 1~3 parts of stearic acid, carrying out ultrasonic reaction fully, washing with water, and drying to obtain modified bismuth oxide;
the temperature of the heat treatment in the fifth step is 310 to 320 ℃.
2. The preparation method of the artificial graphite composite anode material for the lithium ion battery according to claim 1, wherein the silane coupling agent is KH570.
3. The preparation method of the artificial graphite composite anode material for the lithium ion battery as claimed in claim 1, wherein the mass fraction of the aqueous solution of sodium persulfate in the second step is 35 to 40%.
4. The method for preparing the artificial graphite composite negative electrode material for the lithium ion battery as claimed in claim 1, wherein the ultrasonic power in S13 is 550-650W, and the ultrasonic time is 15-25min.
5. The preparation method of the artificial graphite composite negative electrode material for the lithium ion battery as claimed in claim 1, wherein the stirring temperature in the stirring dispersion treatment in the fourth step is 55 to 65 ℃, the stirring time is 15 to 25min, and the stirring speed is 500 to 700r/min.
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