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CN118851176B - Preparation method of modified hard carbon negative electrode material, negative electrode sheet containing the same, and sodium ion battery - Google Patents

Preparation method of modified hard carbon negative electrode material, negative electrode sheet containing the same, and sodium ion battery Download PDF

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CN118851176B
CN118851176B CN202411321533.XA CN202411321533A CN118851176B CN 118851176 B CN118851176 B CN 118851176B CN 202411321533 A CN202411321533 A CN 202411321533A CN 118851176 B CN118851176 B CN 118851176B
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hard carbon
negative electrode
coupling agent
modified
silane coupling
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CN118851176A (en
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赵文文
张惠
钟世昌
董思晓
贾玲
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Wuxi Zhaona New Energy Technology Co ltd
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract

The invention belongs to the technical field of secondary batteries, and discloses a preparation method of a modified hard carbon negative electrode material, a negative electrode plate containing the modified hard carbon negative electrode material and a sodium ion battery. The preparation method comprises the following steps of carrying out in-situ modification on a hard carbon precursor by using a silane coupling agent, and carrying out dehydration condensation reaction on Si-OH bonds generated after silane hydrolysis and hydroxyl groups, carboxyl groups and other groups on the surface of the hard carbon material to obtain the modified hard carbon negative electrode material. The modification of the silane coupling agent has a remarkable enhancement effect on the sodium storage performance of the material, gram capacity can be remarkably improved, the silane coupling agent and functional groups on the surface of the hard carbon material are subjected to a coupling reaction in the modification process, side reactions in the primary charging process are reduced, and meanwhile, the wettability of electrolyte is improved by introducing the silane coupling agent, so that the primary coulomb efficiency and the cycle performance can be remarkably improved. In addition, the silane coupling agent can inhibit the growth of SEI films and improve the rate capability of the material.

Description

Preparation method of modified hard carbon negative electrode material, negative electrode plate containing modified hard carbon negative electrode material and sodium ion battery
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a preparation method of a modified hard carbon negative electrode material, a negative electrode plate containing the modified hard carbon negative electrode material, and a sodium ion battery.
Background
Hard carbon has received much attention in recent years as a novel carbon negative electrode material due to its unique microstructure and electrochemical properties. The hard carbon has higher reversible capacity, good multiplying power performance, excellent safety and lower cost in the application field of sodium ion batteries, and has wide application prospect. But also has the defects that 1, the first coulomb efficiency is low, and the hard carbon material can generate larger irreversible capacity loss in the first charge and discharge process, and the first coulomb efficiency is generally only about 70% -85%. This is mainly because the surface of the hard carbon material forms an irreversible solid electrolyte interface film (SEI film), consuming a large amount of lithium ions. 2. The safety problem is that the hard carbon material can generate irreversible electrochemical reaction under the high potential condition to generate a large amount of heat, so that thermal runaway reaction is easy to generate, and a certain potential safety hazard exists.
Aiming at the characteristics of low first effect and poor safety performance of the hard carbon anode material, the common technical direction is that ① uses metal (Pb, al and the like) to modify the material, but the metal cost is high, and higher processing temperature is required in the processing process, so that the cost of the material is increased. ② The method has the advantages that the morphology of the material is optimized, ball milling, coating and the like are usually used in common material sphericizing processes, the method can cause the change of the material structure, thereby affecting the effect of lithium/sodium storage and further affecting the capacity exertion and the cycle life of a battery, or the method is used for directly synthesizing spherical precursors, and the method has high cost and low yield and is not suitable for mass production. Therefore, in order to overcome the above disadvantages, further research on the hard carbon material is needed, the comprehensive performance of the hard carbon material is improved, and the wide application of the hard carbon material in sodium ion batteries is facilitated.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of a modified hard carbon negative electrode material, a negative electrode plate containing the modified hard carbon negative electrode material, and a sodium ion battery. The modified hard carbon negative electrode material prepared by the invention can effectively improve the multiplying power performance, capacity and cycle performance of the sodium battery.
The invention provides a preparation method of a modified hard carbon anode material.
Specifically, the preparation method of the modified hard carbon anode material comprises the following steps:
And (3) carrying out in-situ modification on the hard carbon precursor by using a silane coupling agent, and carrying out dehydration condensation reaction on Si-OH bonds generated after silane hydrolysis and hydroxyl groups, carboxyl groups and other groups on the surface of the hard carbon material to obtain the modified hard carbon negative electrode material.
More specifically, the preparation method of the modified hard carbon anode material comprises the following steps:
crushing and carbonizing a hard carbon precursor to obtain carbide;
Hydrolyzing the silane coupling agent to obtain silane coupling agent hydrolysate;
Carrying out condensation reaction on the carbide to be modified and the hydrolysate of the silane coupling agent under the condition that the pH value is 2-4, washing and drying after the reaction is finished, and obtaining the modified hard carbon anode material;
The chemical formula of the silane coupling agent is Y-R-Si (OR) 3, wherein Y is a saturated non-oxygen-containing functional group, and R is an alkyl group.
Preferably, the hard carbon precursor includes at least one of biomass raw material, resin raw material, mineral raw material. The biomass raw material comprises coconut shells, rice hulls, peanut shells, lignin or saccharides and the like, the resin raw material comprises phenolic resin and/or epoxy resin, and the mineral raw material comprises asphalt or coal.
Preferably, the carbonization temperature is 550-700 ℃, and the carbonization time is 2-6 hours.
Preferably, the pickling process is to use dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid and hydrofluoric acid for pickling. If dilute hydrochloric acid with the concentration of 1% -5% is used, carrying out acid washing treatment according to the mass ratio of the dilute hydrochloric acid to the carbide of (1:1) - (5:1).
Preferably, the carbide further comprises a step of an activation treatment before the pickling, the activation treatment comprising a physical activation treatment and a chemical activation treatment. The physical activation treatment is carried out for 1-5 h under the action of water vapor according to the mass ratio of water vapor to carbide of (1:1.5) - (1:4) at 600-900 ℃. The chemical activation treatment is carried out for 1-5 h under the action of alkali according to the mass ratio of the carbide to the alkali of (1:1.5) - (1:4) at 600-900 ℃. The carbide is activated to form pore canal structure and pores with different particle diameters, such as a large number of micropores or mesopores (with adjustable pore diameter), in the hard carbon material, so that the specific surface area of the material can be improved. The generation of pores can increase the storage of sodium ions in the material and increase the capacity, and the contact of the hard carbon material and the silane coupling agent can also be increased due to the high specific surface area, after the silane coupling agent is added, si-OH is generated after the coupling agent is hydrolyzed, and condensation reaction is carried out between Si-OH and oxygen-containing functional groups on the surface of the hard carbon material, so that the functional groups with good binding property with organic matters are generated on the surface of the carbon material. The structure can reduce side reaction of the hard carbon material and the electrolyte solvent/additive, stabilize the SEI film and greatly improve the coulombic efficiency and the cycle stability of the material. The base may be potassium hydroxide, sodium hydroxide, or the like.
Preferably, when the hard carbon precursor is a mineral raw material (e.g., coal pitch), a step of pre-oxidation treatment is further included before the activation treatment of the carbide. Specifically, the pre-oxidation treatment process is that the carbide is placed in oxygen and inert atmosphere, and pre-oxidation treatment is carried out for 1-4 hours at 450-650 ℃ to obtain a pre-oxidized material. The carbide prepared by taking mineral raw materials as hard carbon precursors has regular carbon atom arrangement, a preoxidation procedure is added in the preparation process, and the C-C bond between oxygen and a carbon layer is subjected to oxidation reaction, so that the carbon layer structure can be adjusted, the disorder degree of carbon is increased, the storage capacity of the material for sodium ions is improved finally, and the rate performance of a sodium battery is improved.
Preferably, the silane coupling agent is an aminosilane and/or a vinylsilane. The aminosilane comprises gamma-aminopropyl triethoxysilane (KH 550) and the vinyl silane comprises vinyl triethoxysilane.
Preferably, the mass ratio of the silane coupling agent to the carbide to be modified is (0.1:99.9) - (1.5:98.5). Further preferably, the mass ratio of the silane coupling agent to the carbide to be modified is (0.5:99.5) - (1.5:98.5), and more preferably, the mass ratio of the silane coupling agent to the carbide to be modified is (0.8:99.2) - (1.2:98.8).
Preferably, the silane coupling agent is hydrolyzed by dissolving the silane coupling agent in a solvent, and hydrolyzing for 20-60 min at a pH of 2-4. The solvent comprises alcohols (ethanol, methanol) or weak acids (acetic acid, oxalic acid). The mass of the silane coupling agent accounts for 1% -30% of the mass of the solvent.
Preferably, the pH of the condensation reaction is 2-3, the temperature of the condensation reaction is 20-120 ℃, and the time of the condensation reaction is 30 min-3 h.
The invention also provides a preparation method of the silicon dioxide coated hard carbon material.
Specifically, the preparation method of the silicon dioxide coated hard carbon material comprises the following steps:
and carrying out high-temperature curing treatment on the modified hard carbon negative electrode material prepared by the preparation method to form a silicon dioxide coating layer, so as to prepare the silicon dioxide coated hard carbon material.
Preferably, the high-temperature curing treatment is carried out for 1-5 hours at 500-900 ℃ in an inert atmosphere, and further preferably, the high-temperature curing treatment is carried out for 1.5-3 hours at 700-900 ℃ in an inert atmosphere.
The invention also provides a sodium ion battery anode material, which comprises the modified hard carbon anode material prepared by the preparation method of the modified hard carbon anode material or the silicon dioxide coated hard carbon material prepared by the preparation method of the silicon dioxide coated hard carbon material. Compared with the conventional hard carbon material, the modified hard carbon material or the silicon dioxide coated hard carbon material is used as the negative electrode material of the sodium ion battery, and the surface of the modified hard carbon negative electrode material provided by the invention has extremely small oxygen-containing functional groups, because the silane coupling agent is introduced to perform coupling reaction with the original oxygen-containing functional groups on the surface of the hard carbon material, the side reaction of oxygen and electrolyte is removed, the lipophilic group at the other end of the coupling agent has better compatibility with the electrolyte, the wettability of the electrolyte is improved, in addition, the coupling agent can inhibit the growth of SEI (solid electrolyte interface) films, and the multiplying power performance of the material is improved.
The invention also provides a negative electrode plate which comprises the sodium ion battery negative electrode material. The negative electrode sheet comprises a negative electrode current collector and a negative electrode material layer combined on the surface of the current collector, wherein the negative electrode material layer comprises a negative electrode active material, a binder and a conductive agent, and the negative electrode active material comprises the modified hard carbon negative electrode material or the silicon dioxide coated hard carbon material.
The negative electrode current collector is a structure or part for collecting current, and can be various materials suitable for being used as a negative electrode current collector of a sodium ion battery in the field. For example, the negative electrode current collector includes, but is not limited to, a metal foil or the like, and more specifically includes, but is not limited to, an aluminum foil or the like.
The negative electrode plate provided by the invention can be prepared according to the conventional method of the negative electrode plate, for example, the negative electrode active material, the conductive agent and the binder are prepared into slurry according to the proportion, and then the slurry is coated, rolled and die-cut under a certain surface density to obtain the negative electrode plate. In the slurry, the anode active material accounts for 90-99wt%, the conductive agent accounts for 0.05-5wt%, and the binder accounts for 0.5-5wt%. Wherein the binder includes but is not limited to at least one of SBR, PAA, PI, PAN, PVDF, and the conductive agent includes but is not limited to at least one or more of carbon black (such as Super-P, KS-6), VGCF, multi-wall CNTs, single-wall CNTs, and the like, and is not repeated herein.
The invention also provides a sodium ion battery, which comprises a positive plate, the negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals.
The positive plate comprises a positive current collector and a positive active material layer coated on at least one surface of the positive current collector, wherein the positive active material in the positive active material layer can be a positive material for a conventional sodium ion battery, such as a layered composite metal oxide. The positive current collector may be various materials suitable in the art as a positive current collector for sodium ion batteries, for example, the positive current collector includes, but is not limited to, a metal foil or the like, more specifically includes, but is not limited to, an aluminum foil or the like.
The separator may be a variety of materials suitable for sodium ion battery separators in the art, for example, the separator includes, but is not limited to, polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fibers, and the like in combination with one or more of them.
Compared with the prior art, the invention has the beneficial effects that:
Compared with the conventional hard carbon material, the modification of the silane coupling agent has a remarkable enhancement effect on the sodium storage performance of the material, gram capacity can be remarkably improved, the silane coupling agent and the functional groups on the surface of the hard carbon material are subjected to a coupling reaction in the modification process, side reactions in the primary charging process are reduced, meanwhile, the wettability of electrolyte is improved due to the introduction of the silane coupling agent, and the primary coulomb efficiency and the cycle performance can be remarkably improved. In addition, the silane coupling agent can inhibit the growth of SEI films and improve the rate capability of the material.
Drawings
FIG. 1 is a flow chart of example 3 for preparing a coupling agent modified hard carbon material;
FIG. 2 is a schematic diagram showing hydrolysis of gamma-aminopropyl triethoxysilane in examples 1-5;
FIG. 3 is a schematic diagram of the reaction of modified hard carbon with gamma-aminopropyl triethoxysilane in examples 1-5;
FIG. 4 XRD patterns of hard carbon materials before and after modification of comparative example 1 (before modification) and example 1 (after modification);
FIG. 5 is an SEM image of a modified hard carbon material of example 1;
FIG. 6 is an FTIR chart of a hard carbon material before and after modification of comparative example 1 (before modification) and example 1 (after modification);
FIG. 7 shows charge and discharge curves before and after modification of comparative example 1 (before modification) and example 1 (after modification);
fig. 8 is a silica-coated hard carbon material prepared in example 12.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
In order to make the technical scheme and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
Example 1
The embodiment provides a preparation method of a modified hard carbon anode material, which comprises the following steps:
S01, selecting coconut shells as raw materials, and crushing to obtain coconut shell powder, wherein the particle size D50 is 1-3 mm;
s02, performing high-temperature carbonization treatment on the coconut shell powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coconut shells;
S03, pickling the carbonized coconut shell obtained in the step S02 in 3% of dilute HCl, wherein the mass ratio of the dilute HCl to the carbonized coconut shell is 1:1;
S04, leaching with 50 times deionized water to be neutral to obtain carbonized coconut shells to be modified;
s05, dissolving a silane coupling agent gamma-aminopropyl triethoxysilane into absolute ethyl alcohol and deionized water (the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1), regulating the pH value to 2 by adopting 3% dilute hydrochloric acid, and mixing for 20min to hydrolyze (a hydrolysis schematic diagram is shown in figure 2) to obtain a silane coupling agent hydrolysate with the mass fraction of 3%;
s06, mixing the carbonized coconut shell to be modified with the silane coupling agent gamma-aminopropyl triethoxysilane hydrolysate obtained in S05 (the mass ratio of the carbonized coconut shell to the silane coupling agent to be modified is 99.5:0.5), and carrying out condensation reaction under the condition that the pH=2, the reaction temperature is 120 ℃ and the reaction time is 1h, wherein the reaction schematic diagram of the gamma-aminopropyl triethoxysilane modified hard carbon is shown in figure 3;
And S07, cleaning and drying the material obtained in the step S06 by using deionized water, and crushing (D50: 5-6 mu m) to remove magnetism to obtain the coupling agent modified hard carbon material.
Example 2
The embodiment provides a preparation method of a modified hard carbon anode material, which comprises the following steps:
S01, selecting coal tar pitch as a raw material, and crushing to obtain coal tar pitch powder, wherein the particle size D50 is 1-3 mm;
S02, carrying out high-temperature carbonization treatment on the coal tar pitch powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the time is 2.5 hours, so as to obtain carbonized coal tar pitch;
S03, pre-oxidizing the carbonized coal tar pitch prepared in the step S02 under the condition of 1% oxygen and 99% inert atmosphere, wherein the treatment temperature is 500 ℃ and the treatment time is 2 hours, so as to obtain a pre-oxidized material;
s04, pickling the pre-oxidized material obtained in the step S03 in 3% dilute HCl, wherein the mass ratio of the acid liquor to the pre-oxidized material is 1:1;
S05, leaching with 50 times deionized water to be neutral and drying to obtain carbonized coal pitch to be modified;
S06, dissolving a silane coupling agent gamma-aminopropyl triethoxysilane in absolute ethyl alcohol and deionized water (the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1), regulating the pH value to 2 by adopting 3% dilute hydrochloric acid, mixing for 20min, and hydrolyzing to obtain a silane coupling agent hydrolysate with the mass fraction of 3%;
S07, mixing the carbonized coal tar pitch to be modified with the silane coupling agent gamma-aminopropyl triethoxysilane hydrolysate obtained in the step S06 (the mass ratio of the carbonized coal tar pitch to the silane coupling agent to be modified is 99.5:0.5), and carrying out condensation reaction under the reaction condition that the pH=2, the reaction temperature is 120 ℃ and the reaction time is 1h;
And S08, cleaning and drying the material obtained in the step S07 by using deionized water solution, and crushing (D50: 5-6 mu m) to remove magnetism to obtain the coupling agent modified hard carbon material.
Example 3
The embodiment provides a preparation method of a coupling agent modified hard carbon anode material (a flow chart of the preparation method is shown in fig. 1), which comprises the following steps:
S01, selecting coconut shells as raw materials, and crushing to obtain coconut shell powder, wherein the particle size D50 is 1-3 mm;
S02, performing high-temperature carbonization treatment on the coconut shell powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coconut shells;
s03, activating the carbonized coconut shell obtained in the step S02 under the condition of water vapor, wherein the treatment condition is that the water vapor is nitrogen=1.5:1, the temperature is 850 ℃, and the time is 3 hours, so as to obtain the activated carbonized coconut shell;
s04, pickling the carbonized coconut shell obtained in the S03 in 3% dilute HCl, wherein the mass ratio of the acid liquor to the carbonized coconut shell is 1:1;
s05, leaching with 50 times deionized water to be neutral and drying to obtain carbonized coconut shells to be modified;
S06, dissolving a silane coupling agent gamma-aminopropyl triethoxysilane in absolute ethyl alcohol and deionized water (the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1), regulating the pH value to 2 by adopting 3% dilute hydrochloric acid, mixing for 20min, and hydrolyzing to obtain a silane coupling agent hydrolysate with the mass fraction of 3%;
s07, mixing the carbonized coconut shell to be modified with the silane coupling agent gamma-aminopropyl triethoxysilane hydrolysate obtained in the step S06 (the mass ratio of the carbonized coconut shell to be modified to the silane coupling agent is 99.5:0.5), and carrying out condensation reaction under inert atmosphere, wherein the pH=2, the reaction temperature is 120 ℃ and the reaction time is 1h;
And S08, cleaning and drying the material obtained in the step S07 by using deionized water solution, and crushing (D50: 5-6 mu m) to remove magnetism to obtain the coupling agent modified hard carbon material.
Example 4
The embodiment provides a preparation method of a hard carbon anode material, which comprises the following steps:
S01, selecting coal tar pitch as a raw material, and crushing to obtain coal tar pitch powder, wherein the particle size D50 is 1-3 mm;
s02, carrying out high-temperature carbonization treatment on the coal tar pitch powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coal tar pitch;
S03, pre-oxidizing the carbonized coal tar pitch prepared in the step S02 under the condition of 1% oxygen and 99% inert atmosphere, wherein the treatment temperature is 500 ℃ and the treatment time is 2 hours, so as to obtain a pre-oxidized material;
S04, mixing the pre-oxidized material obtained in the step S03 with KOH (the mass ratio of the pre-oxidized material to the KOH is 1:3), and then activating the mixture, wherein the treatment condition is that the temperature is 850 ℃ and the time is 3 hours, so as to obtain an activated pre-oxidized material;
s05, pickling the preoxidized material obtained in the step S04 in 3% dilute HCl, wherein the mass ratio of the acid liquor to the preoxidized material is 1:1;
S06, leaching with 50 times deionized water to be neutral, drying, crushing (D50: 5-6 mu m) and demagnetizing to obtain the carbonized coal pitch to be modified.
S07, dissolving a silane coupling agent gamma-aminopropyl triethoxysilane in absolute ethyl alcohol and deionized water (the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1), regulating the pH value to 2 by adopting 3% dilute hydrochloric acid, mixing for 20min, and hydrolyzing to obtain a silane coupling agent hydrolysate with the mass fraction of 3%;
S08, mixing the carbonized coal tar pitch to be modified with the silane coupling agent gamma-aminopropyl triethoxysilane hydrolysate obtained in the S07 (the mass ratio of the carbonized coal tar pitch to be modified to the silane coupling agent is 99.5:0.5), and carrying out condensation reaction under inert atmosphere, wherein the pH=2, the reaction temperature is 120 ℃, and the reaction time is 1h;
and S09, cleaning and drying the material obtained in the step S08 by using deionized water solution, and crushing (D50: 5-6 mu m) to remove magnetism to obtain the coupling agent modified hard carbon material.
Example 5
S01, selecting commercial hard carbon materials (colali, type 2) as raw materials, calibrating by using the button cell testing method, wherein the gram capacity is 285mAh/g, and the initial effect is 86%;
S02, pickling the commercial hard carbon material in S01 in 3% dilute HCl, wherein the mass ratio of the acid liquor to the commercial hard carbon material is 1:1;
s03, leaching with 50 times deionized water to be neutral and drying to obtain carbide to be modified;
S04, dissolving a silane coupling agent gamma-aminopropyl triethoxysilane into absolute ethyl alcohol and deionized water (the mass ratio of the absolute ethyl alcohol to the deionized water is 1:1), regulating the pH value to 2 by adopting 3% dilute hydrochloric acid, mixing for 20min, and hydrolyzing to obtain a silane coupling agent hydrolysate with the mass fraction of 3%;
S05, mixing the modified carbide with the silane coupling agent gamma-aminopropyl triethoxysilane hydrolysate obtained in the step S04 (the mass ratio of the carbide to be modified to the silane coupling agent is 99.5:0.5), and carrying out condensation reaction under inert atmosphere, wherein the pH=2, the reaction temperature is 120 ℃, and the reaction time is 1h;
And S06, cleaning and drying the material obtained in the step S05 by using deionized water solution, crushing (D50: 5-6 mu m) and demagnetizing to obtain the coupling agent modified hard carbon material.
Example 6
Unlike example 1, the silane coupling agent used in S05 was 3-methylpropyltrimethoxysilane.
Example 7
Unlike example 1, the ratio of charred coconut husk to silane coupling agent in S06 was 99:1.
Example 8
Unlike example 1, the pH in S06 was 2, the treatment temperature was 80℃and the treatment time was 2h.
Example 9
Unlike example 1, example 9 further includes step S08 of subjecting the obtained coupling agent-modified hard carbon material obtained in example 1 to a high-temperature curing treatment under an inert atmosphere at 600℃for 2 hours.
Example 10
Unlike example 1, the silane coupling agent type was replaced with an equivalent amount of vinyltriethoxysilane.
Example 11
Unlike example 2, the coupling agent-modified hard carbon material obtained in example 2 was subjected to a high-temperature curing treatment under an inert atmosphere at a temperature of 800 ℃ for 2 hours.
Example 12
Unlike example 4, the coupling agent-modified hard carbon material obtained in example 4 was subjected to a high-temperature curing treatment under an inert atmosphere at a temperature of 800℃for 2 hours.
Example 13
Unlike example 9, when the coupling agent-modified hard carbon material was subjected to the high-temperature curing treatment, the temperature of the high-temperature curing treatment was adjusted to 800 ℃.
Comparative example 1
The comparative example provides a preparation method of a hard carbon anode material, comprising the following steps:
S01, selecting coconut shells as raw materials, and crushing to obtain coconut shell powder, wherein the particle size D50 is 1-3 mm;
S02, performing high-temperature carbonization treatment on the coconut shell powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coconut shells;
S03, cleaning the carbonized coconut shells obtained in the step S02 in 3% dilute HCl, wherein the ratio of acid liquor to the carbonized coconut shells is 1:1;
S04, leaching with 50 times deionized water to be neutral, drying, and crushing (D50: 5-6 mu m) to remove magnetism, thereby obtaining the hard carbon material.
Comparative example 2
The comparative example provides a preparation method of a hard carbon anode material, comprising the following steps:
S01, selecting coal tar pitch as a raw material, and crushing to obtain coal tar pitch powder, wherein the particle size D50 is 1-3 mm;
s02, carrying out high-temperature carbonization treatment on the coal tar pitch powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coal tar pitch;
s03, pre-oxidizing the carbonized coal tar pitch prepared in the step S02 under the condition of 1% oxygen and 99% inert atmosphere, wherein the treatment temperature is 500 ℃ and the treatment time is 2 hours, so as to obtain a pre-oxide;
S04, cleaning the pre-oxide obtained in the step S03 in 3% dilute HCl, wherein the ratio of acid liquor to the pre-oxide is 1:1;
S05, leaching with 50 times deionized water to be neutral, drying, crushing (D50: 5-6 mu m) and demagnetizing to obtain the hard carbon material.
Comparative example 3
The comparative example provides a preparation method of a hard carbon anode material, comprising the following steps:
S01, selecting coconut shells as raw materials, and crushing to obtain coconut shell powder, wherein the particle size D50 is 1-3 mm;
S02, performing high-temperature carbonization treatment on the coconut shell powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coconut shells;
s03, activating the carbonized coconut shell obtained in the step S02 under the condition of water vapor, wherein the treatment condition is that the water vapor is nitrogen=1.5:1, the treatment temperature is 850 ℃ and the treatment time is 3 hours, so as to obtain the activated carbonized coconut shell;
s04, cleaning the carbonized coconut shells obtained in the step S03 in 3% dilute HCl, wherein the ratio of acid liquor to the carbonized coconut shells is 1:1;
S05, leaching with 50 times deionized water to be neutral, drying, crushing (D50: 5-6 mu m) and demagnetizing to obtain the hard carbon material.
Comparative example 4
The comparative example provides a preparation method of a hard carbon anode material, comprising the following steps:
S01, selecting coal tar pitch as a raw material, and crushing to obtain coal tar pitch powder, wherein the particle size D50 is 1-3 mm;
s02, carrying out high-temperature carbonization treatment on the coal tar pitch powder prepared in the step S01 in an inert atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 2.5 hours, so as to obtain carbonized coal tar pitch;
s03, pre-oxidizing the carbonized coal tar pitch prepared in the step S02 under the condition of 1% oxygen and 99% inert atmosphere, wherein the treatment temperature is 500 ℃ and the treatment time is 2 hours, so as to obtain a pre-oxide;
S04, mixing the pre-oxide obtained in the step S03 with KOH (the mass ratio of the material to be treated to the KOH is 1:3), and then activating the mixture, wherein the treatment condition is that the temperature is 850 ℃ and the time is 3 hours, so as to obtain the activated pre-oxide;
S05, cleaning the pre-oxide obtained in the step S04 in 3% dilute HCl, wherein the ratio of acid liquor to the pre-oxide is 1:1;
s06, leaching with 50 times deionized water to be neutral, drying, crushing (D50: 5-6 mu m) and demagnetizing to obtain the hard carbon material.
Comparative example 5
The procedure is as in example 1 except that the pH in S05 of example 1 is adjusted to 7.5.
Comparative example 6
Unlike example 1, the silane coupling agent γ -aminopropyl triethoxysilane in example 1 was replaced with an equal amount of epoxysilane (KH 560).
Comparative example 7
Unlike example 1, the pH in S05 was adjusted to 5.
The materials obtained in examples 1 to 13 and comparative examples 1 to 7 were used as negative electrode materials for sodium ion batteries and applied to negative electrode sheets.
The preparation method of the negative plate comprises the steps of mixing a negative electrode material, SBR+CMC and SP-P according to the mass ratio of 95:3:2 under the same condition to obtain negative electrode slurry, coating the negative electrode slurry on the surface of an aluminum foil, and carrying out vacuum drying for 12h at 110 ℃ after rolling to obtain the negative plate.
The obtained negative electrode sheet is applied to a sodium ion battery. Sodium foil is used as an anode, polypropylene is used as a diaphragm, and nonaqueous electrolyte is used as electrolyte (the specific preparation method comprises the steps of mixing ethylene carbonate and ethylmethyl carbonate in a volume ratio of 3:7, adding NaPF 6 to form electrolyte, and the concentration of NaPF 6 is 1 mol/L), so that the sodium ion battery is manufactured, and the specific process can be seen in the existing preparation method and is not repeated here.
And testing gram capacity, first cycle efficiency, charging multiplying power and cycle life of the obtained sodium ion battery.
The specific test method comprises the following steps:
(1) Gram capacity and first charge-discharge efficiency test, namely, placing a sodium ion battery in an environment of 25 ℃ for standing for 8 hours, discharging to 0V at 0.xC (x=1-3), discharging to 0V at 0.0xC (x=1-3), and charging to 2V at 0.xC (x=1-3) for 5 minutes. Taking the charging capacity as the final gram capacity value, and taking the ratio of the charging capacity to the discharging capacity as the first charging and discharging efficiency value.
(2) And (3) testing the charge rate and the cycle performance, namely placing the sodium ion battery in an environment with the temperature of 25 ℃, charging to 4.0V at an xC (1C-3C) constant current and constant voltage, discharging to 1.5V at a cut-off current of 0.05C at a constant current of 0.7C, recording the charge and discharge in one step as a cycle number, and recording the number of cycles when the cycle is repeated until the capacity retention rate is lower than 80%.
The test results are shown in Table 1.
TABLE 1
From the results of table 1, it can be seen that examples 1 and 3, examples 2 and 4, examples 3 and 4 add an activation step, the material structure is adjusted based on the original material structure, and pores are formed on the premise of not affecting the carbon atom arrangement, so that dendritic pore structures are generated in the material particles, and the proportion of micropores (< 2 nm) reaches 95%. The creation of a pore structure can store more lithium/sodium ions, providing more capacity.
In comparative examples 1 and 2, in example 2, since the arrangement of carbon atoms in the coal pitch is more regular, a preoxidation process is added in the preparation process, and the oxidation reaction of the c—c bond between oxygen and the carbon layer is aimed at occurring, so as to adjust the carbon layer structure, increase the disorder degree of carbon, further improve the storage capacity of the material for sodium ions finally, and improve the rate capability of the lithium/sodium battery.
Comparative examples 1 and 1, examples 2 and 2, examples 3 and 3, and examples 4 and 4, examples 1 to 4 were modified with a coupling agent on the surface of a hard carbon material. Before modification, the surface of the hard carbon material is provided with a large amount of oxygen-containing groups such as hydroxyl groups, carboxyl groups and the like, the oxygen-containing groups are easy to react with the electrolyte to cause irreversible capacity loss, so that the initial coulomb efficiency is low, and in addition, the oxygen-containing functional groups react with the electrolyte to generate gas to influence the electrochemical performance of the battery. Fig. 4 and 6 respectively describe XRD, FTIR spectra, fig. 5 are SEM images of the modified materials of comparative example 1 (before modification) and example 1 (after modification), fig. 4 and 6 show that the oxygen-containing functional group disappears after modification, the silane coupling agent has reacted with the functional group on the hard carbon surface, and the arrangement and structure of carbon atoms are not changed after modification. Fig. 7 shows charge and discharge curves before and after modification of comparative example 1 (before modification) and example 1 (after modification), and it is apparent from fig. 7 that the gram capacity of the battery can be significantly improved after modification. According to the analysis reason, the silane coupling agent firstly undergoes hydrolysis reaction (reaction shown in figure 2) and then undergoes polycondensation reaction (reaction shown in figure 3) with the functional groups on the surface of the hard carbon, so that the hidden danger of low initial efficiency and poor circulation caused by contact of oxygen and electrolyte is removed, and meanwhile, the other end of the silane coupling agent has stronger reaction inertia, better compatibility with the electrolyte and higher conductivity. Therefore, the hard carbon material modified by the silane coupling agent has higher first coulomb efficiency on one hand, and improves the infiltration with electrolyte on the other hand, reduces the probability of side reaction, so the cycle performance is better.
Comparative example 1 and example 6, the gamma-aminopropyl triethoxysilane nitrogen-containing groups used in example 1 have a stronger polarity, and thus have higher conductivity, and the battery has better rate performance.
In comparison between example 1 and example 7, after the coupling agent content is increased in example 7, the hard carbon surface functional groups are reacted more thoroughly, so that both the initial effect and the cycle performance are improved.
In comparative examples 1 and 9, examples 2 and 11, examples 4 and 12, examples 9,11 and 12 were subjected to high temperature treatment, and molecules on the surface of hard carbon were degraded by heating to form silica, which was coated on the surface of the material (fig. 8, the surface of the material was dense and smooth, while the surface of the uncoated material was rough and had holes (fig. 5)), which had a certain inhibition effect on the expansion of the material during charge and discharge, and the wettability of the electrolyte was also good, so that the capacity and cycle performance were good. The material also eliminates interference of oxygen-containing functional groups, so that capacity is improved. The presence of the coating increases the contact path with the electrolyte, and therefore the magnification is reduced.
In comparative example 10 and example 1, the amino group in contact with the electrolyte in example 1 has a strong polarity and does not react with the electrolyte components, so that the rate performance is good. The inertia of vinyl is better, so that the stability of the surface of the material after long-term circulation is better, the capacity and the initial effect are better, and the circulation performance of the battery is also better.
In comparative examples 13 and 9, the heat treatment temperature was increased to more thoroughly form the silica layer and simultaneously remove the remaining organic functional groups on the surface of the hard carbon material, thereby improving the rate performance and improving the cycle performance.
In comparative examples 1 and 5, the silane coupling agent does not undergo hydrolysis reaction (rightward in fig. 2) under alkaline conditions, and condensation reaction occurs to generate alcohol and ether products, and in the subsequent reaction process, the silane coupling agent has more side reactions with the electrolyte, so that the capacity, the first effect and the cycle performance are poor. The effect on the rate performance is small.
In comparative examples 1 and 6, after the epoxy coupling agent hydrolyzes and modifies the carbon material, the reaction product is esters, and the functional groups of the esters have more side reactions with the electrolyte in the subsequent reaction process, so that the capacity, the first effect and the cycle performance are poor. The effect on the rate performance is small.
In comparative examples 1 and 7, the pH of the solvent in comparative example 7 was increased, and the reaction as shown in FIG. 2 was not sufficiently performed, so that the amount of the silane coupling agent attached to the hard carbon material was reduced, and the modifying effect on the hard carbon was weakened. Therefore, the capacity is lowered and the rate performance is also deteriorated. The amino functional groups on the hard carbon surface are reduced, and thus stability with the electrolyte is lowered, and cycle performance is lowered. FIG. 2 shows a reversible reaction, wherein the reaction is more advantageous to the right when the pH is smaller in a certain range, so that the hydrolysis reaction product of the coupling agent is smaller when the pH is increased, and the hydroxyl group is smaller, so that the amount of the coupling agent which can react with hard carbon is reduced. The modified hard carbon has fewer lipophilic groups on the surface, and has more side reactions during the first charge and discharge, which is manifested by small capacity and reduced first effect. Since less lipophilic groups conduct ions and the like less than in example 1, the rate performance is also deteriorated.
In conclusion, the gram capacity of the sodium ion battery provided by the invention is greater than or equal to 273mAh/g, and the capacity retention rate is not lower than 80% and the number of circulative turns is greater than or equal to 95. The negative electrode material for the sodium ion battery provided by the invention can be prepared by multiple control of the hard carbon precursor, the hard carbon material, the silane coupling agent and the acid in the preparation process, has better comprehensive chemical property, combines the multiplying power performance, the capacity and the cycle performance, and particularly provides various choices for the sodium ion battery in the field of high multiplying power requirements for the multiplying power performance.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (9)

1.一种改性硬碳负极材料的制备方法，其特征在于，包括以下步骤：1. A method for preparing a modified hard carbon negative electrode material, characterized in that it comprises the following steps: 将硬碳前驱体粉碎、碳化，得到碳化物；crushing and carbonizing a hard carbon precursor to obtain a carbide; 将硅烷偶联剂水解，得到硅烷偶联剂水解液；hydrolyzing the silane coupling agent to obtain a silane coupling agent hydrolyzate; 将所述碳化物酸洗，得到待改性炭化物；再将所述待改性炭化物与所述硅烷偶联剂水解液在pH为2～4、温度为20～120℃的条件下进行缩合反应，反应结束后，经洗涤、干燥，制得改性硬碳负极材料；The carbide is acid-washed to obtain a carbide to be modified; the carbide to be modified is subjected to a condensation reaction with the silane coupling agent hydrolyzate at a pH of 2 to 4 and a temperature of 20 to 120° C. After the reaction is completed, the carbide is washed and dried to obtain a modified hard carbon negative electrode material; 所述硅烷偶联剂的化学式为Y-R-Si(OR)3，其中，Y为饱和的非含氧官能团，R为烷基；The chemical formula of the silane coupling agent is YR-Si(OR) 3 , wherein Y is a saturated non-oxygen-containing functional group and R is an alkyl group; 所述硅烷偶联剂和所述待改性炭化物的质量比为(0.1:99.9)～（1.5:98.5）。The mass ratio of the silane coupling agent to the carbonized material to be modified is (0.1:99.9) to (1.5:98.5). 2.根据权利要求1所述的改性硬碳负极材料的制备方法，其特征在于，所述碳化物在进行酸洗之前还包括活化处理的步骤，所述活化处理包括物理活化处理或化学活化处理。2. The method for preparing a modified hard carbon negative electrode material according to claim 1 is characterized in that the carbide further includes an activation treatment step before acid washing, and the activation treatment includes a physical activation treatment or a chemical activation treatment. 3.根据权利要求2所述的改性硬碳负极材料的制备方法，其特征在于，所述物理活化处理的过程为在水蒸气的作用下，按照水蒸气与所述碳化物的质量比为（1:1.5）～（1:4），于600～900℃下，活化处理1～5h；所述化学活化处理的过程为在碱的作用下，按照所述碳化物与所述碱的质量比为（1:1.5）～（1:4），于600～900℃下，活化处理1～5h。3. The method for preparing a modified hard carbon negative electrode material according to claim 2 is characterized in that the physical activation treatment process is to perform an activation treatment at 600-900°C for 1-5 hours under the action of water vapor, with a mass ratio of water vapor to the carbide being (1:1.5) to (1:4); and the chemical activation treatment process is to perform an activation treatment at 600-900°C for 1-5 hours under the action of alkali, with a mass ratio of the carbide to the alkali being (1:1.5) to (1:4). 4.根据权利要求1～3中任一项所述的改性硬碳负极材料的制备方法，其特征在于，所述缩合反应的时间30min～3h。4 . The method for preparing a modified hard carbon negative electrode material according to claim 1 , wherein the condensation reaction time is 30 min to 3 h. 5.一种二氧化硅包覆硬碳材料的制备方法，其特征在于，包括以下步骤：5. A method for preparing a silicon dioxide-coated hard carbon material, characterized in that it comprises the following steps: 将权利要求1～4中任一项所述的改性硬碳负极材料的制备方法制备的改性硬碳负极材料，进行高温固化处理，形成二氧化硅包覆层，制得二氧化硅包覆硬碳材料。The modified hard carbon negative electrode material prepared by the method for preparing the modified hard carbon negative electrode material according to any one of claims 1 to 4 is subjected to high temperature curing treatment to form a silicon dioxide coating layer to prepare a silicon dioxide coated hard carbon material. 6.根据权利要求5所述的二氧化硅包覆硬碳材料的制备方法，其特征在于，所述高温固化处理的过程为：于惰性气氛、500～900℃下，高温固化处理1～5h。6. The method for preparing a silica-coated hard carbon material according to claim 5, characterized in that the high-temperature curing process is: high-temperature curing treatment in an inert atmosphere at 500 to 900°C for 1 to 5 hours. 7.一种钠离子电池负极材料，其特征在于，包括权利要求1～4中任一项所述的改性硬碳负极材料的制备方法制备的改性硬碳负极材料或权利要求5或6所述的二氧化硅包覆硬碳材料的制备方法制备的二氧化硅包覆硬碳材料。7. A negative electrode material for a sodium ion battery, characterized in that it comprises a modified hard carbon negative electrode material prepared by the preparation method of a modified hard carbon negative electrode material according to any one of claims 1 to 4 or a silica-coated hard carbon material prepared by the preparation method of a silica-coated hard carbon material according to claim 5 or 6. 8.一种负极片，其特征在于，包括权利要求7所述的钠离子电池负极材料。8. A negative electrode sheet, characterized in that it comprises the sodium ion battery negative electrode material according to claim 7. 9.一种钠离子电池，其特征在于，包括正极片、权利要求8所述的负极片和间隔于所述正极片与所述负极片之间的隔膜。9. A sodium ion battery, comprising a positive electrode sheet, the negative electrode sheet according to claim 8, and a separator between the positive electrode sheet and the negative electrode sheet.
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