CN115986116B - A modified hard carbon negative electrode material and its preparation method and application - Google Patents
A modified hard carbon negative electrode material and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种改性硬炭负极材料及其制备方法、应用。其包括下述步骤：S1将碳质材料与交联剂混合反应，制得交联后碳质材料，将交联后碳质材料进行碳化处理；S2S1所得物料和改性剂微波辅助混合，碳化处理，制得改性硬炭负极材料；其中，改性剂为银盐和锂盐，银盐和锂盐的质量比为1:1‑1:0.3。本发明制备方法简单，成本低；所得改性硬炭负极材料中掺杂元素分布均匀性好，具有稳定的结构，有利于提高其快速嵌锂的能力使得电池具有优异的电化学性能，例如优异的首次库伦效率、倍率性能、循环性能、高倍率下的可逆容量及容量保持率。
The present invention discloses a modified hard carbon negative electrode material and a preparation method and application thereof. It comprises the following steps: S1 mixing a carbonaceous material with a cross-linking agent to react, obtaining a cross-linked carbonaceous material, and carbonizing the cross-linked carbonaceous material; S2 S1 the obtained material and the modifier are mixed with microwaves, carbonized, and a modified hard carbon negative electrode material is obtained; wherein the modifier is a silver salt and a lithium salt, and the mass ratio of the silver salt to the lithium salt is 1:1-1:0.3. The preparation method of the present invention is simple and low in cost; the obtained modified hard carbon negative electrode material has good uniformity of doping element distribution and a stable structure, which is beneficial to improving its ability to quickly insert lithium so that the battery has excellent electrochemical properties, such as excellent first coulombic efficiency, rate performance, cycle performance, reversible capacity at high rate, and capacity retention rate.
Description
Technical Field
The invention relates to a modified hard carbon anode material, a preparation method and application thereof.
Background
The consumer electronics and power automobile fields are increasingly in need of fast charging. Graphite, which is a widely used negative electrode material for lithium ion batteries, has been increasingly disadvantageous in terms of rapid deintercalation of lithium ions. The stability of the fast charge scenario to the negative electrode material structure is also a challenge.
Hard carbon has a rich pore structure, which is widely focused, and the structure can be kept stable and no particle expansion phenomenon exists in the process of rapid deintercalation of ions. Some hard carbon blending technologies have been used to solve the bottleneck problems of lithium precipitation, poor dynamics and the like in the graphite fast charging process. And compared with the theoretical capacity of graphite 372mAh/g, the lithium storage capacity of the hard carbon is higher, and the capacity of the negative electrode end can be improved after the hard carbon is added.
However, hard carbon itself is less conductive than graphite, and exhibits a large space for improvement in rate performance. Conventional methods for improving the rate capability of hard carbon, such as the reduction of particle size in patent EP3360182B1, shorten the inter-particle transport distance, but may have the disadvantages of more electrolyte consumption and reduced initial efficiency. Metal doping can also improve conductivity, but is highly desirable for process control. How to obtain a hard carbon anode material with simple preparation method, excellent initial coulombic efficiency and rate capability is a problem to be solved in the field.
Disclosure of Invention
The invention solves the technical problem that the preparation process is complex and cannot have excellent first coulombic efficiency and multiplying power performance in the preparation of the hard carbon negative electrode material in the prior art, and provides a modified hard carbon negative electrode material, and a preparation method and application thereof.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of a modified hard carbon anode material, which comprises the following steps:
S1, mixing and reacting a carbonaceous material with a crosslinking agent to obtain a crosslinked carbonaceous material, and carbonizing the crosslinked carbonaceous material;
Mixing the material obtained in S2S 1 with a modifier in a microwave-assisted manner, and sintering to obtain the modified hard carbon anode material;
Wherein the modifier is silver salt and lithium salt, and the mass ratio of the silver salt to the lithium salt is 1:1-1:0.3.
In S1, the carbonaceous material may be one or more of conventional in the art, such as phenolic resin, epoxy resin, furfural resin, peanut shell, crayfish shell, anthracite coal, pitch, corncob, rice husk, glucose, tapioca flour, and the like, such as phenolic resin and/or glucose.
In a preferred embodiment, the carbonaceous material is a phenolic resin and glucose in a mass ratio of (0.2-4): 1, such as 1:4, 2:3, 3:2 or 4:1.
In S1, the mass ratio of the carbonaceous material and the crosslinking agent is preferably 100 (5-30), for example 100:15.
In S1, the cross-linking agent may be a substance conventionally used in the art to enable cross-linking of carbonaceous materials, such as maleic acid and/or methanol.
When the crosslinking agent is a mixture of maleic acid and methanol, the molar ratio of maleic acid to methanol is preferably 1:0.8 to 1.2, for example 1:1.
In S1, the crosslinking agent is generally added in the form of a solution.
When the crosslinking agent is used in the form of a solution, the solvent in the solution is typically water.
When the crosslinking agent is used in the form of a solution, the concentration of the crosslinking agent may be conventional in the art, for example, 3mol/L.
In S1, the temperature of the mixing reaction is preferably 50-180℃such as 120 ℃.
In S1, the mixing reaction time is preferably 2 to 12 hours.
In S1, the mixing reaction may be performed under normal pressure.
In S1, after the mixing reaction, the mixture is generally cooled naturally.
In S1, after the mixing reaction, the crosslinked carbonaceous material is preferably subjected to pulverization and classification.
Wherein the particle size of the crushed and graded product is preferably 5-10 μm.
In S1, the temperature of the carbonization treatment is preferably 500-575 ℃.
In S1, the carbonization treatment is preferably performed for 2 to 4 hours, for example, 3 hours.
In S1, the pressure of the carbonization treatment is preferably 1MPa to 1.3MPa.
In S1, the carbonization treatment atmosphere is generally an inert atmosphere or a nitrogen atmosphere. The inert atmosphere may be an argon atmosphere.
In S1, the rate of raising the temperature to the carbonization treatment temperature is preferably 2 to 3℃per minute, for example 2.3℃per minute.
In S1, the carbonized material is naturally cooled.
In S1, after the carbonization treatment, grinding and sieving are preferably performed. The particle size of the crushed and sieved material is preferably 3-5 μm, for example 3 μm, 4 μm or 5 μm.
In S2, the mass ratio of the modifier to the carbonaceous material is preferably 0.01-0.1:100, e.g. 0.05:100.
In S2, the silver salt is preferably one or more of silver nitrate, silver acetate, silver chloride, silver carbonate and silver phosphate, for example silver acetate.
In S2, the lithium salt is preferably one or more of lithium nitrate, lithium acetate, lithium chloride and lithium carbonate, for example lithium acetate.
In S2, the mass ratio of the silver salt and the lithium salt is preferably 1:1 to 1:0.3, for example 1:0.3, 1:0.5, 1:0.8 or 1:1.
In S2, the frequency of the microwave-assisted mixing is preferably 1400-1600MHz, for example 1500MHz.
In S2, the time of the microwave-assisted mixing is preferably 10 to 14 hours, for example 12 hours.
In S2, the sintering pressure may be 101Kpa-100Pa, for example 101KPa.
In S2, the sintering temperature may be 1000-1200 ℃, e.g. 1120 ℃.
In S2, the sintering time may be 2-3 hours, for example 3 hours.
In S2, the rate of heating to the sintering temperature is preferably 2-3℃per minute, for example 3 ℃.
The invention also provides a modified hard carbon anode material prepared by the preparation method.
The invention also provides application of the modified hard carbon anode material in a lithium ion battery.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
The preparation method is simple and low in cost, and the obtained modified hard carbon anode material has good uniformity of doping element distribution and a stable structure, and is beneficial to improving the capability of rapid lithium intercalation so that the battery has excellent electrochemical properties, such as excellent first coulombic efficiency, rate capability, cycle performance, reversible capacity under high rate and capacity retention rate.
Drawings
FIG. 1 is a scanning electron microscope image of the modified hard carbon negative electrode material prepared in example 1.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
S1, weighing 3000g of phenolic resin and 2000g of glucose, dissolving the phenolic resin and the glucose in a mixed aqueous solution of 3.0mol/L of maleic acid and 3mol/L of methanol (the molar ratio of the maleic acid to the methanol is 1:1), heating to 120 ℃ under normal pressure to carry out a crosslinking reaction for 12 hours, and naturally cooling to room temperature after the reaction is finished, wherein the mass ratio of carbonaceous materials (phenolic resin and glucose) to crosslinking agents (maleic acid and methanol) is 100:15;
Putting the obtained product into jet milling, milling to obtain a carbonaceous raw material with a particle size of 5-10 μm, heating to 500 ℃ at a rate of 2.3 ℃ per min under nitrogen atmosphere of 1.0MPa, maintaining for 3h, naturally cooling to room temperature, and milling and sieving to obtain a material with a particle size of 5 μm;
And (2) carrying out microwave-assisted mixing on 5200g of the carbonaceous material pretreated by S2 and an aqueous solution of a modifier (the modifier is silver acetate and lithium acetate, the water consumption is 200mL, the mass ratio of the silver acetate to the lithium acetate is 1:1, the modifier is 2.5 g), wherein the microwave frequency is 1500MHz, the microwave treatment time is 12h, and the uniformly mixed material is heated to 1120 ℃ at a speed of 3 ℃ per minute, and the pressure is 101KPa, so as to obtain the modified hard carbon anode material.
Example 2
Example 2 is different from example 1 only in that the mass ratio of silver acetate to lithium acetate is 1:0.8, and other operations and conditions are the same as in example 1.
Example 3
Example 3 is different from example 1 only in that the mass ratio of silver acetate to lithium acetate is 1:0.5, and other operations and conditions are the same as in example 1.
Example 4
Example 4 was compared to example 1, except that the mass ratio of silver acetate to lithium acetate was 1:0.3, and the other operations and conditions were the same as in example 1.
Example 5
Example 5 was compared with example 2, except that the raw material was changed to phenol resin 2000 and glucose 3000g, and the other operations and conditions were the same as in example 2.
Example 6
Example 6 was compared with example 2, except that the raw materials were changed to phenolic resin 1000 and glucose 4000g, and the other operations and conditions were the same as in example 2.
Example 7
Example 7 was compared to example 2, except that the starting material was changed to 4000g of phenolic resin and 1000g of glucose, and the other operations and conditions were the same as in example 2.
Example 8
Example 8 was different from example 2 only in that the crushed particle diameter after the carbonaceous material was carbonized after the crosslinking in step S1 was 3 μm, and the other operations and conditions were the same as in example 2.
Example 9
Example 9 was different from example 2 only in that the crushed particle diameter was 4 μm after the carbonaceous material was carbonized after the crosslinking in step S1, and the other operations and conditions were the same as in example 2.
Comparative example 1
Comparative example 1 in comparison with example 1, there was no step of modifying silver acetate and lithium acetate, and other operations and conditions were the same as in example 1.
Comparative example 2
Comparative example 2 was compared to example 1, except that the mass ratio of silver acetate to lithium acetate was 1:0 (i.e., only silver acetate was modified), and the other operations and conditions were the same as in example 1.
Comparative example 3
Comparative example 3 is different from comparative example 2 only in that no microwave-assisted mixing is performed, and other operations and conditions are the same as in example 1.
Comparative example 4
Comparative example 4 was compared to example 1, except that the mass ratio of silver acetate to lithium acetate was 0:1 (i.e., only lithium acetate was modified), and the other operations and conditions were the same as in example 1.
Effect example 1 physical Property test of modified hard carbon negative electrode Material
The modified hard carbon negative electrode materials obtained in examples 1 to 4 and comparative examples 1 to 4 were measured for particle size D50, tap density, and specific surface area (BET). The instruments and models used for the index test are shown in table 1, and specific data are shown in table 2.
TABLE 1
| Test index | Instrument and model thereof |
| Particle size D50 | Laser particle size distribution instrument MS3000 |
| Tap density | Tap tester BT-302 |
| Specific surface area (BET) | Specific surface area measuring instrument NOVATouch2000,2000 |
FIG. 1 is a scanning electron microscope image of the modified hard carbon negative electrode material prepared in example 1.
Effect example 2
The modified hard carbon cathode materials obtained in examples 1-7 are used as active materials to be assembled into button cells, the ratio of the active materials to the binder to the conductive agents is 95:3:2, the button cells are stirred at a certain speed to prepare slurry, the slurry is coated on copper foil with the thickness of 5 mu m, then the drying and rolling are carried out, the pole pieces with the diameter of 16mm are cut, and the surface density of the active materials is 100g/m 2. The CR2032 coin cell was prepared using lithium sheets as counter electrode, 1.0M LiPF 6 (EC/dmc=1/1, v/v) as electrolyte and PP-based film as separator.
The half-cell was subjected to a first efficiency test on a battery tester of type ArbinBT, U.S. Pat. No. 2000, with a charge-discharge voltage ranging from 0.005V to 2.0V and a charge-discharge rate of 0.1c, 1c=500 mA/g. The test results are shown in Table 2.
The half-cell was subjected to rate performance on a battery tester of ArbinBT in the united states under the test conditions of 0.1C for charge current, 1 c=500 mA/g and 0-5.0C for discharge current. Capacity recovery = R xC(x＝1,2,3,5))/R0.1C x 100%, where R x is xC discharge capacity, R 0.1 is first 0.1C charge capacity, 1c = 500mA/g. The test results are shown in Table 3.
TABLE 2 physicochemical parameters and first Effect of the products of examples 1-9, comparative examples 1-4
In the first effect, in the embodiments 1 to 4 of the present invention, the mass ratio of Ag to Li in the embodiment 2 is 1:0.8, and the first effect is the best, and the second effect is the embodiments 1, 4 and 3. As can be seen from comparison of examples 6, 5, 2 and 7 of the present invention, the mass ratio of phenolic resin to glucose was 0.25, 0.6, 1.5 and 4, respectively, and the first effect of example 2 was optimal when the rate performance was increased and then decreased. As can be seen from a comparison of examples 2 and 8-9 of the present invention, the particle size of example 8 is the smallest and the first effect of example 2 is the best. The first time efficiency is the worst without Ag and Li modification in comparative example 1. Comparative examples 2 to 4 have only a single Ag or Li modification, and have first time efficiency better than comparative example 1, but still are inferior to inventive examples 1 to 9, and comparative example 4 has first time effect better than comparative examples 1 to 3.
TABLE 3 rate performance and capacity recovery data for examples 1-9, comparative examples 1-4
In the case of the rate performance, the rate performance was the worst without Ag and Li modification in comparative example 1. In comparative examples 2 to 3, only Ag was modified, and comparative example 2 with microwave treatment had better effect than comparative example 3 without microwave treatment. In the examples 1 to 4 of the present invention, the mass ratio of Ag to Li in the example 4 was 1:0.3, and the rate performance was optimal, and the examples 3 and 1 to 2 were followed. As is clear from comparison of examples 6, 5, 2 and 7 of the present invention, the mass ratio of the phenolic resin to glucose was 0.25, 0.6, 1.5 and 4, respectively, and the rate performance of example 2 was optimal when the rate performance was increased and then decreased. As is clear from comparison of examples 2 and 8-9 of the present invention, example 8 has the smallest particle size and the best rate performance.
In comparative example 1, no Ag or Li modification was used for the capacity recovery rate, and the capacity recovery rate was the worst. Comparative examples 2-4 have only a single Ag or Li modification and have better capacity recovery than comparative example 1, but still are inferior to inventive examples 1-4. Examples 1-9 were excellent in capacity recovery, ranging from 98.6 to 99.9%.
Claims (20)
1. The preparation method of the modified hard carbon anode material is characterized by comprising the following steps of:
S1, mixing and reacting a carbonaceous material with a crosslinking agent to obtain a crosslinked carbonaceous material, and carbonizing the crosslinked carbonaceous material;
And mixing the material obtained in the step S2S 1 with a modifier in a microwave-assisted manner, and sintering to obtain the modified hard carbon negative electrode material, wherein the modifier is silver salt and lithium salt, the mass ratio of the silver salt to the lithium salt is 1:1-1:0.3, and the sintering temperature is 1000-1200 ℃.
2. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S1, the carbonaceous material is one or more of phenolic resin, epoxy resin, furfural resin, peanut shell, crayfish shell, anthracite, asphalt, corncob, rice husk, glucose and tapioca flour;
and/or, in S1, the mass ratio of the carbonaceous material to the cross-linking agent is 100 (5-30);
and/or in S1, the cross-linking agent is maleic acid and/or methanol.
3. The method for preparing a modified hard carbon negative electrode material according to claim 2, wherein in S1, the carbonaceous material is phenolic resin and/or glucose;
And/or, in S1, the mass ratio of the carbonaceous material to the crosslinking agent is 100:15;
and/or in S1, when the cross-linking agent is a mixed solution of maleic acid and methanol, the molar ratio of the maleic acid to the methanol is 1:0.8-1.2.
4. The method for producing a modified hard carbon negative electrode material according to claim 3, wherein in S1, when the carbonaceous material is a phenolic resin and glucose, the mass ratio of the phenolic resin to glucose is (0.2-4): 1;
And/or, in S1, when the cross-linking agent is a mixed solution of maleic acid and methanol, the molar ratio of the maleic acid to the methanol is 1:1.
5. The method for preparing a modified hard carbon negative electrode material according to claim 4, wherein in S1, when the carbonaceous material is phenolic resin and glucose, the mass ratio of phenolic resin to glucose is 1:4, 2:3, 3:2 or 4:1.
6. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S1, the temperature of the mixing reaction is 50-180 ℃;
and/or, in S1, the time of the mixing reaction is 2-12h;
and/or, in S1, after the mixing reaction, crushing and grading the crosslinked carbonaceous material.
7. The method for preparing a modified hard carbon negative electrode material according to claim 6, wherein in S1, the temperature of the mixing reaction is 120 ℃;
and/or in S1, the particle size of the crushed and graded product is 5-10 mu m.
8. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S1, the carbonization treatment is performed at a temperature of 500-575 ℃;
and/or, in S1, the carbonization treatment time is 2-4h;
And/or, in S1, the pressure of the carbonization treatment is 1MPa-1.3MPa;
and/or in S1, raising the temperature to the carbonization treatment temperature at a rate of 2-3 ℃ per minute.
9. The method for preparing a modified hard carbon negative electrode material according to claim 8, wherein in S1, the carbonization treatment is performed for 3 hours;
and/or, in S1, the rate of heating to the carbonization treatment temperature is 2.3 ℃ per minute.
10. The method for producing a modified hard carbon negative electrode material according to claim 1, wherein in S1, the carbonization treatment is followed by pulverization and sieving.
11. The method for producing a modified hard carbon negative electrode material according to claim 10, wherein in S1, the particle size of the pulverized and sieved material is 3 to 5 μm.
12. The method for producing a modified hard carbon negative electrode material according to claim 11, wherein in S1, the particle size of the pulverized and sieved material is 3 μm, 4 μm or 5 μm.
13. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S2, the mass ratio of the modifier to the carbonaceous material is 0.01-0.1:100;
And/or in S2, the silver salt is one or more of silver nitrate, silver acetate, silver chloride, silver carbonate and silver phosphate;
and/or in S2, the lithium salt is one or more of lithium nitrate, lithium acetate, lithium chloride and lithium carbonate.
14. The method for preparing a modified hard carbon negative electrode material according to claim 13, wherein in S2, the mass ratio of the modifier to the carbonaceous material is 0.05:100;
And/or, in S2, the silver salt is silver acetate;
And/or, in S2, the lithium salt is lithium acetate.
15. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S2, the mass ratio of the silver salt to the lithium salt is 1:1 to 1:0.3.
16. The method for preparing a modified hard carbon negative electrode material according to claim 15, wherein in S2, the mass ratio of the silver salt to the lithium salt is 1:0.3, 1:0.5, 1:0.8 or 1:1.
17. The method for preparing a modified hard carbon negative electrode material according to claim 1, wherein in S2, the frequency of the microwave-assisted mixing is 1400-1600MHz;
and/or in S2, the microwave-assisted mixing time is 10-14h;
And/or, in S2, the sintering pressure is 101KPa-100Pa;
and/or, in S2, the sintering temperature is 1120 ℃;
And/or, in S2, sintering for 2-3h;
and/or in S2, the rate of heating to the sintering temperature is 2-3 ℃ per minute.
18. The method for preparing a modified hard carbon negative electrode material according to claim 17, wherein in S2, the frequency of the microwave-assisted mixing is 1500MHz;
and/or, in S2, the time of the microwave-assisted mixing is 12h;
And/or, in S2, sintering for 3 hours;
and/or, in S2, heating to the sintering temperature at a rate of 3 ℃ per minute.
19. A modified hard carbon negative electrode material prepared by the preparation method of any one of claims 1 to 18.
20. Use of the modified hard carbon negative electrode material of claim 19 in a lithium ion battery.
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