CN110890538B - Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material - Google Patents

Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material Download PDF

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CN110890538B
CN110890538B CN201911110284.9A CN201911110284A CN110890538B CN 110890538 B CN110890538 B CN 110890538B CN 201911110284 A CN201911110284 A CN 201911110284A CN 110890538 B CN110890538 B CN 110890538B
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silane coupling
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林扬帆
张亚光
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Zhejiang Lichen New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for improving the first coulombic efficiency of a silicon cathode material for a lithium ion battery, which comprises the following steps: (1) measuring the hydroxyl content on the surface of the silicon negative electrode material; (2) grafting a silane coupling agent on the surface of the silicon negative electrode material through organic chemical modification; the silane coupling agent has the general formula R1‑Si‑(OR2)3，R1Selected from inert radicals, R2Selected from methyl or ethyl; addition amount M of silane coupling agent1Calculated by the following formula (1), M1Mass of silane coupling agent, g; m is1Relative molecular mass of the silane coupling agent, g/mol; m2Mass of the silicon negative electrode material, g; and X is the content of hydroxyl on the surface of the silicon negative electrode material, mmol/g. The silicon-based lithium ion battery cathode material prepared by the method has the initial coulombic efficiency of over 90 percent, and is expected to be widely applied to the field of lithium ion batteries.
Figure DDA0002272509870000011

Description

Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a method for improving the first coulombic efficiency of a silicon-based lithium ion battery cathode material.
Background
The requirement of the modern society on clean energy is higher and higher, and the lithium ion battery as a new generation of clean energy plays a very important role in the fields of energy storage, electric vehicles, convenient equipment and the like. However, the development of electric vehicles nowadays has higher and higher requirements on the aspects of safety performance, energy density and the like of lithium ion batteries, and in the field of negative electrodes, the current commercial graphite negative electrode cannot meet the increasing requirements of people due to the lower theoretical specific capacity (340mAh/g), and on the basis, the silicon negative electrode is a new-generation high-capacity lithium ion battery negative electrode material due to the extremely high theoretical specific capacity (4200 mAh/g).
However, silicon also presents challenges as a negative electrode material for lithium ion batteries: firstly, the volume expansion of 300% of silicon can occur after lithium is embedded, so that the pulverization of silicon materials and the damage of a pole piece structure are caused, and finally the electric contact of an active material is lost; secondly, the silicon material has poor conductivity and poor rate capability; and thirdly, the silicon cathode material is difficult to improve the first coulomb efficiency. The first coulombic efficiency is an important parameter in the full cell, and because the lithium provided by the anode is limited, the energy density of the full cell is reduced due to the fact that a large amount of lithium is consumed in the first cycle, and therefore the significance of improving the first coulombic efficiency of the silicon cathode is great.
Chinese patent publication No. CN 109411717 a discloses a prelithiated negative electrode material with high reversible capacity and a method for preparing the same, the method for preparing the silicon negative electrode material includes: step 1, stirring and mixing silicon powder, lithium carbonate powder, graphite carbon materials, grinding aids and the like; and step 2, comparing the negative electrode material obtained by ball milling the mixed powder obtained in the step 1 with corresponding silicon powder, wherein the first coulombic efficiency of the negative electrode material is 5-10% higher.
According to the technical scheme, the silicon negative electrode material, the lithium carbonate powder, the graphite carbon material and the grinding aid are mixed and ball-milled together, so that the silicon negative electrode material is uniformly adsorbed on the surface of the carbon material, and pre-lithiation is carried out through lithium carbonate, and finally the silicon-based lithium ion battery negative electrode material with high initial coulombic efficiency is obtained. Firstly, because a lot of inert materials such as lithium carbonate and grinding aids are introduced into the silicon-based negative electrode material synthesized by the scheme, and low-energy-density materials such as graphite carbon materials have limited silicon material content, the material has low capacity of only about 1000 mAh/g; secondly, the silicon-based lithium ion battery cathode material improves the overall coulombic efficiency in a composite material synthesis mode, and the silicon material does not improve the coulombic efficiency for the first time; and thirdly, lithium carbonate is introduced into the material, and reacts with HF generated in the battery circulation process to generate carbon dioxide to generate gas, so that the safety performance of the battery is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a method for improving the first coulombic efficiency of a silicon-based lithium ion battery cathode material, and the prepared silicon-based lithium ion battery cathode material has the first coulombic efficiency of over 90 percent and is expected to be widely applied to the field of lithium ion batteries.
The specific technical scheme is as follows:
a method for improving the first coulombic efficiency of a silicon-based lithium ion battery negative electrode material comprises the following steps:
(1) measuring the hydroxyl content on the surface of the silicon negative electrode material;
(2) grafting a silane coupling agent on the surface of the silicon negative electrode material through organic chemical modification;
the general formula of the silane coupling agent is R1-Si-(OR2)3In the formula, R1Selected from inert radicals not involved in the degradation of the electrolyte during the cycling of the battery, R2Selected from methyl or ethyl;
the addition amount M of the silane coupling agent1Comprises the following steps:
Figure BDA0002272509850000021
in the formula, M1Mass of silane coupling agent, g; m is1Relative molecular mass of the silane coupling agent, g/mol; m2Mass of the silicon negative electrode material, g; and X is the content of hydroxyl on the surface of the silicon negative electrode material, mmol/g.
In the invention, firstly, the concentration of hydroxyl contained in the surface of the silicon material is calibrated by the existing means for measuring the content of the hydroxyl on the surface; and determining the using amount of the silane coupling agent containing the inert group according to the concentration of the hydroxyl contained in the surface of the silicon material by using a formula (1), and replacing the hydroxyl on the surface of the silicon material with the inert group on the silane coupling agent through organic reaction.
In the invention, the dosage and the type of the silane coupling agent are the key to whether the silicon-based lithium ion battery cathode material can obtain high first coulombic efficiency. Since the silane coupling agent is easy to undergo self-polymerization reaction and generate macromolecules rich in hydroxyl groups, the required dosage of the silane coupling agent needs to be estimated according to the concentration of the hydroxyl groups on the surface of the silicon material, so that the phenomenon that excessive silane coupling agent is deposited on the surface of the silicon material after self-polymerization to cause a large amount of residual hydroxyl groups is prevented. Experiments show that excessive silane coupling agent can increase the content of hydroxyl on the surface of the silicon negative electrode material, and the first coulombic efficiency of the silicon negative electrode material is reduced.
In fact, the dosage of the silane coupling agent is accurately calculated by adopting the following formula (2), the optimal dosage of the silane coupling agent is calculated by adopting the formula (2), and in practical application, the dosage of the silane coupling agent can be floated by 10% from top to bottom on the basis of the dosage obtained by the formula (2), namely the formula (1), and the initial coulomb efficiency of the silicon-based lithium ion battery cathode material can also be improved.
Figure BDA0002272509850000031
In view of the above, the inventors have explained this conclusion by theoretical analysis: hydroxyl on the surface of the silicon negative electrode material can participate in the decomposition reaction of the electrolyte in the battery circulation process, so that the electrolyte is promoted to deposit on the surface of the silicon negative electrode material to form a thick SEI film, a large amount of lithium source provided by the positive electrode is consumed, irreversible capacity is formed, and the first coulombic efficiency of the battery is reduced. And surface hydroxyl groups are replaced by groups which do not participate in electrode reaction through the silane coupling agent containing inert groups, so that the consumption of electrolyte and lithium ions on the surface of the silicon negative electrode material is avoided, and the first coulomb efficiency of the battery is improved.
In the step (1):
the silicon negative electrode material comprises a nano-scale silicon material, a micron-scale silicon material and a porous silicon material.
The determination of the hydroxyl content on the surface of the silicon negative electrode material can adopt the existing detection mode, preferably adopts an acid-base titration method, and specifically comprises the following steps:
adding W mg of silicon negative electrode material into 80mL of 0.05mol/L sodium hydroxide aqueous solution, fully stirring at room temperature for 24 hours, centrifuging, adding phenolphthalein reagent into 10mL of supernate, titrating by using 0.05mol/L hydrochloric acid, and recording the volume of the hydrochloric acid used when the solution changes color as A mL; titrating 10mL of 0.05mol/L sodium hydroxide aqueous solution by using 0.05mol/L hydrochloric acid, and marking the volume of the hydrochloric acid used when the solution changes color as B mL;
the hydroxyl content X on the surface of the silicon negative electrode material is calculated according to the following formula:
Figure BDA0002272509850000041
in the formula, X is the surface hydroxyl content of the silicon negative electrode material, mmol/g, and W is the mass of the silicon negative electrode material, mg.
Generally, the content of hydroxyl on the surface of the silicon negative electrode material is 0.5-10 mmol/g.
In the step (2):
firstly, mixing the silicon negative electrode material with water, then mixing the silane coupling agent with an ethanol solution, finally mixing the silicon negative electrode material and the ethanol solution, and grafting the silane coupling agent on the surface of the silicon negative electrode material after hydrolysis reaction.
Preferably:
the mass volume ratio of the silicon negative electrode material to water is 0.5-500 g/L;
the mass volume ratio of the silane coupling agent to the ethanol is 0.5-500 g/L.
Further preferably:
the mass volume ratio of the silicon negative electrode material to water is 0.5-1.5 g/L;
the mass volume ratio of the silane coupling agent to the ethanol is 0.5-1.5 g/L.
In the present invention, the choice of the type of silane coupling agent is of critical importance, the basic principle being the choice of a silane coupling agent containing an inert group such as R which does not participate in the degradation of the electrolyte during cycling of the battery1Selected from hydrogen group, alkyl group with 1-18 carbon atoms, aromatic group, amino group or fluoro group.
The aromatic group includes phenyl, benzyl, naphthyl, etc.
Preferably, the silane coupling agent is selected from at least one of trimethoxysilane, triethoxysilane, methyltriethoxysilane, N-propyltriethoxysilane, octadecyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, 3-aminopropyltrimethoxysilane, triethoxysilane, triethoxy-1H, 1H,2H, 2H-tridecafluoro-N-octylsilane.
Further preferably, the silane coupling agent is selected from triethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, or octadecyltriethoxysilane. Tests show that the first coulombic efficiency of the nano-scale silicon particles grafted and modified by the four silane coupling agents is higher than 90%, and the initial capacity of more than 3000mAh/g can still be exerted.
Still further preferably, the silane coupling agent is selected from phenyl triethoxysilane, and tests show that the nano-scale silicon particles subjected to grafting modification by the silane coupling agent have the initial coulombic efficiency of over 96 percent and still can exert the initial capacity of over 2500 mAh/g.
Compared with the prior art, the invention has the following advantages:
the invention discloses a method for improving the first coulombic efficiency of a silicon cathode. The pure silicon cathode material treated by the method has the first coulombic efficiency of over 90 percent, and the best coulombic efficiency of 96 percent, and is expected to be widely applied to the field of lithium ion batteries.
Drawings
FIG. 1 shows performance data of half-cells assembled with raw materials of sand-milled nano-silicon negative electrode material;
FIG. 2 is performance data for a half cell assembled with the silicon negative electrode material prepared in example 1;
FIG. 3 is performance data for a half cell assembled with the silicon negative electrode material prepared in example 4;
FIG. 4 is performance data for a half cell assembled with the silicon negative electrode material prepared in example 5;
fig. 5 is performance data for half cells assembled with the silicon anode material prepared in example 6.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
Adding 2mg of nano silicon particles (with the particle size of 150-200 nm) obtained by sand milling into 80mL of 0.05mol/L sodium hydroxide aqueous solution, fully stirring at room temperature for 24 hours, centrifuging, adding a phenolphthalein reagent into 10mL of supernate, and titrating by using 0.05mol/L hydrochloric acid; 10mL of a 0.05mol/L aqueous solution of sodium hydroxide was titrated with 0.05mol/L hydrochloric acid. And finally, calculating by the formula (3) to obtain the content of hydroxyl on the surface of the sand-milled nano silicon to be 5.389 mmol/L. The silane coupling agent selects triethoxysilane with a relative molecular mass of 164, and the mass ratio of the triethoxysilane to the nano-silicon calculated by the formula (2) is 883.80: 3000.
adding 100mg of sand-milled nano silicon particles into 100mL of ultrapure water, uniformly stirring, adding 50mL of ethanol solution in which 29.50mg of triethoxysilane is dissolved, stirring for eight hours, and centrifugally cleaning to obtain a modified silicon negative electrode material, which is marked as S1。
The silicon anode material S prepared in the embodiment1The assembled half cell is tested for the first coulombic efficiency, and the half cell assembled by sanding the nano silicon negative electrode material as the untreated raw material is used as a comparison. Wherein, the silicon cathode material S1The coated cell served as the positive electrode and the lithium sheet as the counter electrode. The proportion of each component in the pole piece is as follows: s170% of negative electrode material, 20% of binder CMC, and 78% of conductive agent SP 10%; the loading amount of the active material on the pole piece is 1-1.5 mg/cm2。
The current used by the battery in the first cycle test is 400mA/g, and the test result of the battery is as follows: the first coulombic efficiency of the untreated sand-milled nano-silicon is 80.2%, and the first discharge capacity is 3358.7mAh/g, as shown in FIG. 1; silicon negative electrode material S prepared in this example1The first coulombic efficiency of (a) was 91.5%, and the first discharge capacity was 3590.6mAh/g, as shown in FIG. 2.
Example 2
The silane coupling agent used in this example was triethoxysilane, and the only difference from example 1 was that the mass ratio of triethoxysilane to nanosilicon was calculated using the case where the float of 10% in formula (1) was raised, that is, the mass ratio of triethoxysilane to nanosilicon was 972.18: 3000.
the half cell assembled in this example was tested to have a first coulombic efficiency of 88.3% and a first discharge capacity of 3224.5mAh/g using the same test conditions as in example 1.
Example 3
The silane coupling agent used in this example was triethoxysilane, and the only difference from example 1 is that the mass ratio of triethoxysilane to nanosilicon was calculated using the case of 10% down-regulation in formula (1), i.e., the mass ratio of triethoxysilane to nanosilicon was 795.42: 3000.
using the same test conditions as in example 1, the half cell assembled in this example was tested to have a first coulombic efficiency of 87.6% and a first discharge capacity of 3341.2 mAh/g.
Example 4
The silane coupling agent adopted in this example is methyltriethoxysilane, and the mass ratio of methyltriethoxysilane to nano-silicon is 959.10 calculated by formula (2): 3000.
100mg of the sand-milled nano-silicon particles obtained in the example 1 are added into 100mL of ultrapure water to be uniformly stirred, 50mL of ethanol solution in which 31.97mg of methyltriethoxysilane is dissolved is added, the mixture is stirred for eight hours and then centrifugally cleaned to obtain a modified silicon negative electrode material, which is marked as S2。
The silicon anode material S prepared in the embodiment2The half-cells were assembled for the first coulombic efficiency test. Wherein, the silicon cathode material S2The coated cell served as the positive electrode and the lithium sheet as the counter electrode. The proportion of each component in the pole piece is as follows: s270% of negative electrode material, 20% of binder CMC, and 78% of conductive agent SP 10%; the loading amount of the active material on the pole piece is 1-1.5 mg/cm2。
The current used by the battery in the first cycle test is 400mA/g, and the test result of the battery is the cathode material S2The first coulombic efficiency of (a) was 92.0%, and the first discharge capacity was 3319.7mAh/g, as shown in FIG. 3.
Example 5
The silane coupling agent adopted in this example is phenyl triethoxysilane, and the mass ratio of the phenyl triethoxysilane to the nano silicon is 1293.30 by calculation according to formula (2): 3000.
100mg of the sand-milled nano-silicon particles obtained in example 1 were added into 100mL of ultrapure water, stirred and mixed uniformly, and 50mL of phenyl triethoxy silicon dissolved with 43.11mg of phenyl triethoxy silicon was addedStirring the alkyl ethanol solution for eight hours, and then centrifugally cleaning to obtain a modified silicon negative electrode material, which is marked as S3。
The silicon anode material S prepared in the embodiment3The half-cells were assembled for the first coulombic efficiency test. Wherein, the silicon cathode material S3The coated cell served as the positive electrode and the lithium sheet as the counter electrode. The proportion of each component in the pole piece is as follows: s370% of negative electrode material, 20% of binder CMC, and 78% of conductive agent SP 10%; the loading amount of the active material on the pole piece is 1-1.5 mg/cm2。
The current used by the battery in the first cycle test is 400mA/g, and the test result of the battery is the cathode material S3The first coulombic efficiency of (a) was 96.6%, and the first discharge capacity was 2791.2mAh/g, as shown in FIG. 4.
Example 6
The silane coupling agent adopted in the present embodiment is octadecyl triethoxysilane, and the mass ratio of octadecyl triethoxysilane to nano silicon is 2231.10 by calculation of formula (2): 3000.
100mg of the sand-milled nano-silicon particles obtained in the example 1 are added into 100mL of ultrapure water to be uniformly stirred, 50mL of ethanol solution in which 74.37mg of octadecyl triethoxysilane is dissolved is added, stirring is carried out for eight hours, centrifugal cleaning is carried out to obtain a modified silicon negative electrode material, and the modified silicon negative electrode material is marked as S4。
The silicon anode material S prepared in the embodiment4The half-cells were assembled for the first coulombic efficiency test. Wherein, the silicon cathode material S4The coated cell served as the positive electrode and the lithium sheet as the counter electrode. The proportion of each component in the pole piece is as follows: s470% of negative electrode material, 20% of binder CMC, and 78% of conductive agent SP 10%; the loading amount of the active material on the pole piece is 1-1.5 mg/cm2。
The current used by the battery in the first cycle test is 400mA/g, and the test result of the battery is as follows: negative electrode material S4The first coulombic efficiency of (a) was 90.5%, and the first discharge capacity was 3598.3mAh/g, as shown in FIG. 5.

Claims (9)

1. A method for improving the first coulombic efficiency of a silicon-based lithium ion battery cathode material is characterized by comprising the following steps:
(1) measuring the hydroxyl content on the surface of the silicon negative electrode material;
(2) grafting a silane coupling agent on the surface of the silicon negative electrode material through organic chemical modification;
the general formula of the silane coupling agent is R1-Si-(OR2)3In the formula, R1Selected from hydrogen group, alkyl group with 1-18 carbon atoms, aryl group or fluoro group, R2Selected from methyl or ethyl;
the addition amount M of the silane coupling agent1Comprises the following steps:
Figure FDA0002988844050000011
in the formula, M1Mass of silane coupling agent, g; m is1Relative molecular mass of the silane coupling agent, g/mol; m2Mass of the silicon negative electrode material, g; x is the hydroxyl content on the surface of the silicon negative electrode material, mmol/g;
the dosage of the silane coupling agent is calculated by adopting the formula, and in practical application, the dosage can be floated by 10 percent on the basis of the dosage obtained by the formula.
2. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to claim 1, wherein in the step (1), the silicon negative electrode material comprises a nano-scale silicon material, a micron-scale silicon material or a porous silicon material.
3. The method for improving the initial coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to claim 1, wherein an acid-base titration method is adopted for measuring the hydroxyl content on the surface of the silicon negative electrode material, and specifically comprises the following steps:
adding W mg of silicon negative electrode material into 80mL of 0.05mol/L sodium hydroxide aqueous solution, fully stirring at room temperature for 24 hours, centrifuging, adding phenolphthalein reagent into 10mL of supernate, titrating by using 0.05mol/L hydrochloric acid, and recording the volume of the hydrochloric acid used when the solution changes color as A mL; titrating 10mL of 0.05mol/L sodium hydroxide aqueous solution by using 0.05mol/L hydrochloric acid, and marking the volume of the hydrochloric acid used when the solution changes color as B mL;
the hydroxyl content X on the surface of the silicon negative electrode material is calculated according to the following formula:
Figure FDA0002988844050000021
in the formula, X is the surface hydroxyl content of the silicon negative electrode material, mmol/g, and W is the mass of the silicon negative electrode material, mg.
4. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to claim 1, wherein in the step (2), the silicon negative electrode material is mixed with water, then the silane coupling agent is mixed with the ethanol solution, finally the silicon negative electrode material and the ethanol solution are mixed, and the silane coupling agent is grafted on the surface of the silicon negative electrode material after hydrolysis reaction.
5. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to claim 4, wherein the method comprises the following steps:
the mass volume ratio of the silicon negative electrode material to water is 0.5-500 g/L;
the mass volume ratio of the silane coupling agent to the ethanol is 0.5-500 g/L.
6. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to claim 1, wherein in the step (2), the silane coupling agent is at least one selected from trimethoxy silane, triethoxy silane, methyl triethoxy silane, N-propyl triethoxy silane, octadecyl triethoxy silane, phenyl triethoxy silane, benzyl triethoxy silane, 3-aminopropyl trimethoxy silane, triethoxy fluoro silane, triethoxy-1H, 1H,2H, 2H-tridecafluoro N-octyl silane.
7. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material as claimed in claim 1, wherein in the step (2), the silane coupling agent is selected from triethoxysilane, methyltriethoxysilane, phenyltriethoxysilane or octadecyltriethoxysilane.
8. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material as claimed in claim 1, wherein in the step (2), the silane coupling agent is selected from phenyltriethoxysilane.
9. The method for improving the first coulombic efficiency of the silicon-based lithium ion battery negative electrode material according to any one of claims 1 to 8, wherein the silicon negative electrode material is selected from a nanoscale silicon material.
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