CN107863510B - Cyano-modified silicon oxide lithium battery negative electrode material and preparation method and application thereof - Google Patents
Cyano-modified silicon oxide lithium battery negative electrode material and preparation method and application thereof Download PDFInfo
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- CN107863510B CN107863510B CN201711014669.6A CN201711014669A CN107863510B CN 107863510 B CN107863510 B CN 107863510B CN 201711014669 A CN201711014669 A CN 201711014669A CN 107863510 B CN107863510 B CN 107863510B
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- 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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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Abstract
The invention relates to a cyano-modified silicon oxide lithium battery cathode material and a preparation method and application thereof, belonging to the technical field of batteries. The cyano-modified silicon oxide lithium battery negative electrode material has a structure shown as the following formula:
. The invention adopts the modification of cyanylation of the surface of the silicon oxide material, and improves the capacity retention after cyclic discharge when the modified material is used as the cathode material of the lithium ion battery.
Description
Technical Field
The invention relates to a cyano-modified silicon oxide lithium battery cathode material and a preparation method and application thereof, belonging to the technical field of batteries.
Background
The lithium ion battery takes a carbon material as a negative electrode and a lithium-containing compound as a positive electrode, no metal lithium exists, and only lithium ions exist, so that the lithium ion battery is formed. The lithium ion battery is a generic term for a battery using a lithium ion intercalation compound as a positive electrode material. When the battery is charged, lithium ions are generated on the positive electrode of the battery, and the generated lithium ions move to the negative electrode through the electrolyte. The carbon as the negative electrode has a layered structure having many pores, and lithium ions reaching the negative electrode are inserted into the pores of the carbon layer, and the more lithium ions are inserted, the higher the charge capacity is. Similarly, when the battery is discharged (i.e., during our use of the battery), lithium ions embedded in the carbon layer of the negative electrode are extracted and move back to the positive electrode. The more lithium ions returned to the positive electrode, the higher the discharge capacity.
There are various negative electrode materials for lithium ion batteries: the first is a carbon negative electrode material: the negative electrode material actually used in lithium ion batteries is basically a carbon material such as artificial graphite, natural graphite, mesocarbon microbeads, petroleum coke, carbon fibers, pyrolytic resin carbon, and the like. The second is a tin-based negative electrode material: the tin-based negative electrode material can be classified into tin oxide and tin-based composite oxide. The oxide refers to the oxide of metallic tin in various valence states. The third is a lithium-containing transition metal nitride negative electrode material. The fourth is an alloy-based negative electrode material: the fifth type of the alloy comprises a tin-based alloy, a silicon-based alloy, a germanium-based alloy, an aluminum-based alloy, an antimony-based alloy, a magnesium-based alloy and other alloys, and is a nanoscale negative electrode material: carbon nanotubes and nano-alloy materials. The sixth nanomaterial is a nano-oxide material: various companies have begun to use nano titanium oxide and nano silicon oxide to be added into the conventional graphite, tin oxide and carbon nanotube, so as to greatly improve the charge and discharge amount and the charge and discharge times of the lithium battery.
CN103199227A discloses a lithium ion battery nano carbon-silicon composite negative electrode material and a preparation method thereof, wherein the nano carbon-silicon composite negative electrode material is a nano particle with the particle size of 20-50 nm; the silicon part is a composite structure of silicon and silicon dioxide prepared from silicon monoxide; the carbon part is prepared from an amphiphilic carbon material; the carbon part is coated on the surface of the silicon part to form a triple composite structure of carbon, silicon dioxide and silicon. CN104362315A discloses a low-cost preparation method of a silicon-carbon composite negative electrode material of a lithium ion battery, which comprises the following steps: (1) purifying a graphite raw material; (2) performing magnesium thermal reduction; (3) removing impurities; (4) coating the surface; (5) carbonizing; thus, after reducing and purifying silicon dioxide in the raw material graphite through a magnesium thermal reaction, a compound of porous silicon and graphite is obtained, and then surface coating is carried out, so that the silicon-carbon composite negative electrode material for the lithium ion battery is obtained.
In the case of a silicon oxide negative electrode material, the capacity of the material is reduced due to electrolyte migration, surface corrosion and the like of silicon oxide during long-term operation.
Disclosure of Invention
The purpose of the invention is: the problem of the conventional silicon oxide lithium ion battery cathode material that the capacitance is reduced after repeated charge and discharge cycles caused by instability due to oxidation of silicon oxide is solved. The technical scheme is as follows: the surface of the silicon oxide is modified by the cyanogen group with higher reaction activation energy, so that the stability of the cathode material of the battery in the operation process is greatly improved, and the capacity retention is improved.
The technical scheme is as follows:
a cyano-modified silicon oxide lithium battery negative electrode material has a structure shown as the following formula:
the preparation method of the cyano-modified silicon oxide lithium battery negative electrode material comprises the following steps:
s1: mixing 15-25 parts by weight of ethyl orthosilicate, 4-8 parts by weight of concentrated ammonia water, 20-35 parts by weight of deionized water and 150-200 parts by weight of ethanol, carrying out hydrolysis reaction, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying;
s2: SiO obtained in S12Dispersing in 150-200 parts of ethanol, adding 10-15 parts of cyanooxysilane modifier shown in formula (I), stirring for reaction, performing centrifugal separation on solids, and washing with ethanol and water in sequence to obtain a cyano-modified silicon oxide lithium battery cathode material;
wherein R1, R2 and R3 are respectively and independently selected from straight-chain or branched alkyl containing 1-10 carbon atoms, and more preferably R1, R2 and R3 are all ethyl or isopropyl.
In the step S1, the temperature of the hydrolysis reaction is 35-40 ℃, and the reaction time is 3-6 h.
In the step S2, the reaction temperature is 25-40 ℃, and the reaction time is 3-5 h.
The mass concentration range of the strong ammonia water is 25-35 wt%.
The application of the cyano-modified silicon oxide lithium battery negative electrode material in improving the cycle capacity retention rate of the lithium ion battery.
Advantageous effects
The invention adopts the modification of cyanylation of the surface of the silicon oxide material, and improves the capacity retention after cyclic discharge when the modified material is used as the cathode material of the lithium ion battery.
Drawings
Fig. 1 is a structure of an anode material provided by the present invention;
FIG. 2 is the molecular structure of a cyano modifier;
fig. 3 is an electron micrograph of the prepared silica particles.
Fig. 4 is a graph showing the results of capacity retention in 300 cycles of the charge and discharge test of the full cell.
Detailed Description
Example 1
The preparation method of the cyano-modified silicon oxide lithium battery negative electrode material comprises the following steps:
s1: mixing 15 parts by weight of ethyl orthosilicate, 25wt% of concentrated ammonia water, 20 parts by weight of deionized water and 150 parts by weight of ethanol, carrying out hydrolysis reaction at the temperature of 35 ℃ for 3 hours, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying;
s2: SiO obtained in S12Dispersing in 150 parts of ethanol, adding 10 parts of (2-cyanoethyl) triethoxysilane, stirring for reaction at 25 ℃ for 3 hours, centrifugally separating the solid, and washing with ethanol and water in sequence to obtain the cyano-modified lithium silicon oxide battery cathode material.
Example 2
The preparation method of the cyano-modified silicon oxide lithium battery negative electrode material comprises the following steps:
s1: mixing 15 parts by weight of ethyl orthosilicate, 4 parts by weight of 25wt% concentrated ammonia water, 20 parts by weight of deionized water and 150 parts by weight of ethanol, carrying out hydrolysis reaction at the temperature of 35 ℃ for 3 hours, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying;
s2: SiO obtained in S12Dispersing in 150 parts of ethanol, adding 10 parts of (2-cyanoethyl) triethoxysilane, stirring for reaction at 25 ℃ for 3 hours, centrifugally separating the solid, and washing with ethanol and water in sequence to obtain the cyano-modified lithium silicon oxide battery cathode material.
Example 3
The preparation method of the cyano-modified silicon oxide lithium battery negative electrode material comprises the following steps:
s1: mixing 20 parts by weight of ethyl orthosilicate, 6 parts by weight of 30wt% concentrated ammonia water, 25 parts by weight of deionized water and 180 parts by weight of ethanol, carrying out hydrolysis reaction at 38 ℃ for 5 hours, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying;
s2: SiO obtained in S12Dispersing in 180 parts of ethanol, adding 12 parts of (2-cyanoethyl) triisopropoxysilane, stirring for reaction at 35 ℃ for 4h, centrifuging the solid, washing with ethanol and water in sequence to obtain the cyano-modified lithium silicon oxide battery cathode material.
Comparative example 1
The difference from example 1 is that: the negative electrode material is not cyano-modified.
The preparation method of the silicon oxide lithium battery negative electrode material comprises the following steps:
mixing 20 parts by weight of ethyl orthosilicate, 6 parts by weight of 30wt% concentrated ammonia water, 25 parts by weight of deionized water and 180 parts by weight of ethanol, carrying out hydrolysis reaction at 38 ℃ for 5 hours, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying to obtain the silicon oxide cathode material.
Performance characterization
The results of the tests of the discharge capacity and the first charge and discharge efficiency of the silicon oxide negative electrode materials in the examples and the comparative examples are shown in table 1. the test method of the half cell is that the silicon oxide negative electrode material, N-methyl pyrrolidone containing 10 wt% of polyvinylidene fluoride and 2wt% of conductive carbon black are uniformly mixed according to the proportion of 90: 8: 2, coated on copper foil, the coated pole piece is put into a vacuum drying oven with the temperature of 110 ℃ for vacuum drying for 4 hours for standby, the simulated cell is assembled in a German Braun glove box filled with argon, the electrolyte is 1M L iPF6+ EC: DEC: DMC 1: 1 (volume ratio), the metal lithium piece is a counter electrode, the electrochemical performance test is carried out on an ArbinBT2000 type cell tester, the charge and discharge voltage range is 0.005-1.0V, and the charge and discharge rate is 0.1C.
TABLE 1
| Discharge capacity (mAh/g) | First charge-discharge efficiency (%) | |
| Example 1 | 1023.1 | 94.5 |
| Example 2 | 989.4 | 94.2 |
| Example 3 | 1103.9 | 95.3 |
| Comparative example 1 | 877.3 | 91.8 |
The silicon oxide negative electrode materials in the examples and the comparative examples were tested by a full cell test method, in which the silicon oxide negative electrode material was used as a negative electrode, lithium cobaltate was used as a positive electrode, and a solution of 1M-L iPF6 EC: DMC: EMC (volume ratio) 1: 1 was used as an electrolyte to assemble a full cell, and an electrical property test was performed, and the capacity retention rate was measured after 300 cycles as shown in fig. 4.
The capacity retention after 300 cycles is shown in table 2.
TABLE 2
| Capacity retention% | |
| Example 1 | 91.3 |
| Example 2 | 90.2 |
| Example 3 | 92.0 |
| Comparative example 1 | 80.2 |
As can be seen from fig. 4, the negative electrode materials of examples 1 to 3 still maintained a high permittivity after 300 discharge cycles, while the silicon oxide material of comparative example 1 still had a problem of large capacitance loss because it was not modified.
Claims (1)
1. The application of the cyano-modified silicon oxide lithium battery negative electrode material in improving the circulating capacity retention rate of the lithium ion battery is characterized in that the cyano-modified silicon oxide lithium battery negative electrode material has a structure shown as the following formula:
the preparation method of the cyano-modified silicon oxide lithium battery negative electrode material comprises the following steps:
s1: mixing 15-25 parts by weight of ethyl orthosilicate, 4-8 parts by weight of concentrated ammonia water, 20-35 parts by weight of deionized water and 150-200 parts by weight of ethanol, carrying out hydrolysis reaction, centrifugally separating out silicon oxide particles after the reaction is finished, washing with water, and carrying out vacuum drying;
s2: SiO obtained in S12Dispersing in 150-200 parts of ethanol, adding 10-15 parts of cyanooxysilane modifier shown in formula (I), stirring for reaction, performing centrifugal separation on solids, and washing with ethanol and water in sequence to obtain a cyano-modified silicon oxide lithium battery cathode material;
wherein R1, R2 and R3 are respectively and independently selected from straight-chain or branched-chain alkyl containing 1-10 carbon atoms;
in the step S1, the temperature of the hydrolysis reaction is 35-40 ℃, and the reaction time is 3-6 h;
in the step S2, the reaction temperature is 25-40 ℃, and the reaction time is 3-5 h;
the mass concentration range of the strong ammonia water is 25-35 wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104362315A (en) * | 2014-10-24 | 2015-02-18 | 东莞市翔丰华电池材料有限公司 | Low-cost preparing method of silicon and carbon compound cathode material for lithium ion battery |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104362315A (en) * | 2014-10-24 | 2015-02-18 | 东莞市翔丰华电池材料有限公司 | Low-cost preparing method of silicon and carbon compound cathode material for lithium ion battery |
| CN104577049A (en) * | 2014-12-26 | 2015-04-29 | 中天科技精密材料有限公司 | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material |
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| Title |
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| 有机溶剂对正硅酸乙酯水解制备二氧化硅微球的影响;毛丹等;《稀有金属材料与工程》;20070831;第36卷;第180-183页 * |
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