CN116779809A - Composite semi-solid SiO negative electrode and preparation method and application thereof - Google Patents
Composite semi-solid SiO negative electrode and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007787 solid Substances 0.000 title abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 19
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
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- 229940005550 sodium alginate Drugs 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 238000005524 ceramic coating Methods 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 61
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- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a composite semi-solid SiO negative electrode, a preparation method and application thereof, wherein the negative electrode material consists of a composite solid electrolyte and SiO which are contacted with each other, and the mass ratio of the composite solid electrolyte to the SiO is (0.5-3) 10; wherein the composite solid electrolyte comprises PEO particles and SBA-15 molecular sieves with the mass ratio of (0.5-3): 1. Compared with the traditional liquid environment and the full solid environment, the composite semi-solid electrolyte presents brand-new interface interaction, effectively relieves the stress and volume change in the charge and discharge process, thereby improving the cycle performance of the silicon monoxide negative electrode, simultaneously avoiding the problem of lithium dendrite short circuit in the electric contact process, overcoming the defects of low ion conductivity and poor mechanical property of PEO-based solid polymer electrolyte in the prior art, and facilitating ion transmission. The assembled battery has good cycle stability and rate capability, and shows smaller impedance and higher lithium ion diffusion power through electrochemical impedance spectroscopy.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes, and relates to a novel anode material, in particular to a composite semi-solid SiO anode, a preparation method and application thereof.
Background
Silicon-based has attracted considerable attention as a lithium ion negative electrode material due to its ultra-high theoretical capacity, low discharge potential, and abundant sources. However, the silicon-based material has huge volume change due to larger stress in the lithium intercalation/deintercalation reaction process, so that the anode material is fragile and easy to crack and easily fall off from a current collector, and the capacity of the electrode is quickly attenuated. The organic liquid electrolyte is one of the indispensable components in the current battery system because of higher ionic conductivity and good wettability, but has lower thermal stability and potential safety hazards such as easy combustion and easy leakage. In order to safely utilize high performance lithium ion batteries, alternatives have been proposed, one of which is to replace the liquid electrolyte with a solid polymer electrolyte having the advantages of low flammability, good processability, high energy density, and no leakage. However, solid polymer electrolytes have problems such as low ionic conductivity, poor wettability, low stability/incompatibility between the electrode and the electrolyte, etc., which may deteriorate performance, and have hampered the development of practical applications.
Silicon monoxide (SiO) is widely focused on due to low price, no toxicity and high theoretical capacity, and is a high-capacity anode material with great development prospect. However, siO materials have limited their wide application because of the problems of volume expansion (about 200%), low initial coulombic efficiency, and the like. The solid electrolyte can well inhibit volume expansion and improve energy density, wherein polyethylene oxide (PEO) is the main choice of the current solid polymer electrolyte, and has the advantages of good flexibility and film forming property, low cost, electrochemical stability and the like. However, PEO has a high crystallinity and low ionic conductivity at room temperature, and there are problems such as short circuit formation due to lithium dendrite growth and loss of contact at the interface. In contrast to solid electrolytes, liquid electrolytes can flow during volume changes to continuously wet the material surface. The organic-inorganic composite solid electrolyte has the characteristics of high ionic conductivity, strong interface adaptability, high mechanical strength and the like, and thus, more development space is displayed in the all-solid-state lithium battery.
Disclosure of Invention
The technical problems to be solved are as follows: in order to overcome the defects in the prior art, the problems that silicon monoxide is subjected to volume change due to larger stress in the lithium intercalation/deintercalation reaction process of a lithium ion battery, the anode material is easy to crack and fall off from a current collector, the capacity of the electrode is rapidly attenuated, and the performance is reduced due to the fact that PEO is taken into consideration as solid electrolyte, the ionic conductivity is low, the wettability is poor and the like are solved. In view of this, the invention provides a composite semi-solid SiO negative electrode, and a preparation method and application thereof.
The technical scheme is as follows: the anode material comprises a composite solid electrolyte and SiO which are in contact with each other, wherein the mass ratio of the composite solid electrolyte to the SiO is (0.5-3) 10; wherein the composite solid electrolyte comprises PEO particles and SBA-15 molecular sieves with the mass ratio of (0.5-3): 1.
The preparation method of the anode material containing the composite semi-solid electrolyte and SiO comprises the following steps:
s1, putting SBA-15 molecular sieve, PEO particles and SiO into a ball milling tank;
s2, ball milling is carried out in an argon atmosphere to obtain the granular anode material containing the composite semi-solid electrolyte and SiO, wherein the anode material has a composite structure with a silicon-based anode coated by the surface layer solid electrolyte.
Preferably, the ball milling time in S2 is 6-12 hours, and the particle size of the obtained particles is 10 nm-10 mu m.
Preferably, the particle size of the particles obtained in S2 is 10nm to 400nm.
The application of the anode material containing the composite semi-solid electrolyte and SiO in preparing the anode of the lithium ion secondary battery.
Preferably, the lithium ion secondary battery anode comprises 50-99.5 wt% of anode material containing composite semi-solid electrolyte and SiO, 0.1-40 wt% of conductive agent and 0.1-40 wt% of binder according to mass percentage.
Preferably, the conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene and carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethyl cellulose and sodium alginate.
Preferably, the lithium ion secondary battery includes a negative electrode prepared from a negative electrode material containing a composite semi-solid electrolyte and SiO, a positive electrode, an electrolyte, and a separator.
Preferably, the positive electrode is any one of lithium cobaltate, lithium manganate, lithium nickelate and lithium iron phosphate; the membrane is any one of an aramid membrane, a non-woven fabric membrane, a polyethylene microporous membrane, a polypropylene-polyethylene double-layer or three-layer composite membrane and a ceramic coating membrane; the electrolyte comprises electrolyte and solvent, wherein the electrolyte is LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) At least one of LiBOB, liCl, liBr, liI; the solvent is at least one of Propylene Carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), 1, 2-dimethoxy ethane (DME), ethylene Carbonate (EC), butylene Carbonate (BC), diethyl carbonate (DEC), ethyl Acetate (EA) and ethylene sulfite (GS).
Preferably, the injection amount of the electrolyte is 50-300% of the total mass of the composite semi-solid electrolyte.
The principle of the composite semi-solid electrolyte and SiO-containing anode material composition of the invention is as follows: silicon monoxide has higher theoretical specific capacity (more than 2000 mAh/g) as a lithium ion battery cathode material, but the larger volume change in the charge and discharge process leads to rapid reduction of the capacity of an electrode; PEO is used as a chain polymer electrolyte, so that the volume change of silicon monoxide caused by larger stress in the lithium intercalation/deintercalation reaction process can be effectively relieved, the PEO has the problems of low ion conductivity, poor wettability and other performance degradation, and the SBA-15 molecular sieve is mixed with PEO, so that the ion conductivity can be effectively improved; a small amount of electrolyte is added to solve the problem of poor contact at the solid-solid interface.
The principle of adopting the anode material containing the composite semi-solid electrolyte and SiO to prepare the battery anode is as follows: the simple preparation process of high-energy ball milling under the protection of argon gas reduces the particle size to nanometer level, so that lithium ions have more transportation ways, the composite semi-solid electrolyte and silicon monoxide are uniformly mixed, the effective contact area of the electrolyte and the cathode material is improved, the volume expansion of silicon oxide in the lithium intercalation process is inhibited, and the cycling stability of the battery is improved.
The beneficial effects are that: 1) Aiming at the problems of large volume change and easy structural damage in the lithium intercalation/deintercalation process of the silicon monoxide negative electrode material, the invention designs and constructs the lithium ion battery negative electrode material containing the composite semi-solid electrolyte, the composite semi-solid electrolyte effectively coats the silicon monoxide, the nano-scale size is beneficial to the diffusion and migration of lithium ions, the stress in the lithium intercalation/deintercalation process of the material is relieved and released, the structural stability of the electrode is maintained, and the preparation principle of the experiment is combined, so that the component of the lithium ion battery negative electrode material with the variable composite semi-solid electrolyte can be regulated; 2) The high-energy ball milling method adopted by the invention is a simple, feasible and industrialized nano material synthesis method, realizes the effective compounding of the silicon monoxide negative electrode material and the composite semi-solid electrolyte PEO and SBA-15, the SBA-15 molecular sieve better improves the conductivity of the PEO chain polymer electrolyte, enhances the electrochemical activity of the composite material, creatively utilizes the synergistic effect among the silicon monoxide, PEO and SBA-15, and fully exerts the advantages of the three. The novel composite semi-solid electrolyte provided by the invention can reduce the risk of liquid leakage, further improve the safety performance of the battery, and is beneficial to the industrialization of the novel composite material in the energy storage field.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a composite material prepared according to example 1 of the present invention, wherein the left image has a size of 2 μm and the right image has a size of 500nm;
FIG. 2 is an electrochemical impedance spectrum of a sample assembled half cell of example 1 prepared in accordance with the present invention;
FIG. 3 is a charge-discharge test curve of a sample assembled half cell according to example 1 of the present invention;
FIG. 4 is an electrochemical cycling test curve of a sample assembled half cell of example 1 prepared in accordance with the present invention;
fig. 5 is a graph showing the rate performance test of the assembled half cell of example 1 prepared according to the present invention.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to the method, steps or conditions of the invention without departing from the spirit and nature of the invention are intended to be within the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
Example 1
0.25g of SBA-15 molecular sieve, 0.265g of PEO particles and 5g of silicon monoxide particles are filled into a ball milling tank, and ball milling is carried out for 10 hours in high energy to obtain the granular lithium ion battery anode material containing the composite semi-solid electrolyte.
Fig. 1 shows the results of scanning electron microscope test of the obtained composite material, and it is clear from the figure that the obtained composite material is granular and has good particle dispersion, and the particle size is below 400nm.
The composite material of example 1 was subjected to electrochemical characterization:
the negative electrode material of the lithium ion battery containing the composite semi-solid electrolyte, which is prepared in the embodiment 1, is prepared by 70 weight percent of acetylene black serving as a conductive agent and 15 weight percent of sodium alginate serving as a binder, and the negative electrode material is uniformly dispersed in deionized water to form slurry, the slurry is uniformly coated on copper foil, and the copper foil is placed in a 50 ℃ oven to be dried for 12 hours. Cutting the dried copper foil coated with active material into 10mm small pieces, testing the battery using conventional CR2032 button cell, using lithium piece as counter electrode, and dripping small amount of LiPF 6 The electrolyte was assembled in a standard glove box to form a secondary battery. Electrochemical performance measurements were made at rest for 12 hours after cell assembly was completed.
The impedance test was performed on the battery composed of the materials of example 1, and it can be seen from fig. 2 that example 1 has very small impedance, which indicates that the composite semi-solid electrolyte has good electrical contact with the negative silicon monoxide, so that the impedance of electron diffusion and charge transfer of the electrode material is small, and the mobility of lithium ions is high.
The battery of example 1 was subjected to the charge-discharge test of the first, second and fifth rings, and the results thereof were seen in fig. 3, and it can be seen that the first coulombic efficiency of example 1 could reach 53.0%, showing excellent performance improvement over the first coulombic efficiency of 35% of single silica, and in addition, the SBA-15 molecular sieve effectively improved the defect of low ion conductivity of PEO-based solid polymer electrolyte and improved the conductivity of PEO.
The battery composed of the material of example 1 was subjected to a cyclic test, and as a result, referring to fig. 4, it can be seen that the material has a high reversible capacity and good cyclic stability during the cyclic process, mainly because the PEO combined with SBA-15 can well inhibit the volumetric expansion of SiO and pulverization of the material during charge and discharge.
The battery composed of the material of example 1 was subjected to the rate performance test, and was charged and discharged at a current density of 100mA/g to 1000mA/g, and then at a current density of 1000mA/g to 100mA/g, and as a result, referring to fig. 5, it can be seen that the material exhibited good cycle reversibility and good rate performance.
Claims (10)
1. The anode material containing the composite semi-solid electrolyte and SiO is characterized in that the anode material consists of the composite solid electrolyte and SiO which are contacted with each other, wherein the mass ratio of the composite solid electrolyte to the SiO is (0.5-3) 10; wherein the composite solid electrolyte comprises PEO particles and SBA-15 molecular sieves with the mass ratio of (0.5-3): 1.
2. The method for preparing a negative electrode material containing a composite semi-solid electrolyte and SiO according to claim 1, comprising the steps of:
s1, putting SBA-15 molecular sieve, PEO particles and SiO into a ball milling tank;
s2, ball milling is carried out in an argon atmosphere to obtain the granular anode material containing the composite semi-solid electrolyte and SiO, wherein the anode material has a composite structure with a silicon-based anode coated by the surface layer solid electrolyte.
3. The method for preparing a negative electrode material containing a composite semi-solid electrolyte and SiO according to claim 2, wherein the ball milling time in S2 is 6 to 12 hours, and the particle size of the obtained particles is 10nm to 10 μm.
4. The method for producing a negative electrode material containing a composite semi-solid electrolyte and SiO according to claim 2, wherein the particle size of the particles obtained in S2 is 10nm to 400nm.
5. The use of the anode material containing composite semi-solid electrolyte and SiO according to claim 1 for the preparation of an anode for a lithium ion secondary battery.
6. The use according to claim 5, wherein the lithium ion secondary battery anode comprises, in mass percent, 50 to 99.5wt% of anode material comprising composite semi-solid electrolyte and SiO, 0.1 to 40wt% of conductive agent, and 0.1 to 40wt% of binder.
7. The use according to claim 6, wherein the conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nanotubes, graphene, carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer, sodium carboxymethyl cellulose and sodium alginate.
8. The use according to claim 5, wherein the lithium ion secondary battery comprises a negative electrode, a positive electrode, an electrolyte and a separator, which are prepared from a negative electrode material comprising a composite semi-solid electrolyte and SiO.
9. The use according to claim 8, characterized in thatThe positive electrode is any one of lithium cobaltate, lithium manganate, lithium nickelate and lithium iron phosphate; the membrane is any one of an aramid membrane, a non-woven fabric membrane, a polyethylene microporous membrane, a polypropylene-polyethylene double-layer or three-layer composite membrane and a ceramic coating membrane; the electrolyte comprises electrolyte and solvent, wherein the electrolyte is LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、LiCF 3 SO 3 、LiN(CF 3 SO 2 ) At least one of LiBOB, liCl, liBr, liI; the solvent is at least one of propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1, 2-dimethoxyethane, ethylene carbonate, butylene carbonate, diethyl carbonate, ethyl acetate and ethylene sulfite.
10. The use according to claim 8, wherein the electrolyte is injected in an amount of 50 to 300% of the total mass of the composite semi-solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310757580.8A CN116779809A (en) | 2023-06-26 | 2023-06-26 | Composite semi-solid SiO negative electrode and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310757580.8A CN116779809A (en) | 2023-06-26 | 2023-06-26 | Composite semi-solid SiO negative electrode and preparation method and application thereof |
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| CN116779809A true CN116779809A (en) | 2023-09-19 |
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| CN202310757580.8A Pending CN116779809A (en) | 2023-06-26 | 2023-06-26 | Composite semi-solid SiO negative electrode and preparation method and application thereof |
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| CN (1) | CN116779809A (en) |
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2023
- 2023-06-26 CN CN202310757580.8A patent/CN116779809A/en active Pending
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