CN114057401B - Selenide glass material and preparation method and application thereof - Google Patents
Selenide glass material and preparation method and application thereof Download PDFInfo
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- CN114057401B CN114057401B CN202111369439.8A CN202111369439A CN114057401B CN 114057401 B CN114057401 B CN 114057401B CN 202111369439 A CN202111369439 A CN 202111369439A CN 114057401 B CN114057401 B CN 114057401B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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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
- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a selenide glass material and a preparation method and application thereof, the selenide glass material comprises active substance glass powder, the raw material of the glass powder comprises a network product selenide MSe with the mass ratio of (10-50) to (30-80) to (10-40) x Transition metal oxide DO y And network exo-oxide AO n ；MSe x Wherein M is one or more selected from Ti, si, sn, pb, P, as, sb, bi, O, S and Te; DO y Wherein D is selected from one or more of Fe, V, zr, sb, mo, cr, nb, ta, ni, co, cu and Mn; AO n Wherein A is selected from one or more of Li, na, K, rb, cs, ca, sr, ba, Y, in, la, zr, th, be, mg, zn, al and Ga. The selenide glass material has the advantages of large specific capacity, high voltage, small first-loop loss rate and the like.
Description
Technical Field
The invention belongs to the technical field of glass materials, and particularly relates to a selenide glass material and a preparation method and application thereof.
Background
The lithium ion battery is a new generation green high-energy battery with excellent performance, and has become one of the key points of high and new technology development. The lithium ion battery has the following characteristics: high voltage, high capacity, low consumption, no memory effect, no public hazard, small volume, small internal resistance, less self-discharge and more cycle times. Because of the above characteristics, lithium ion batteries have been applied to various civil and military fields such as mobile phones, notebook computers, video cameras, digital cameras, and the like.
The main constituent materials of the lithium ion battery include electrolyte, isolating materials, positive and negative electrode materials, and the like. The anode material of the lithium ion battery mainly comprises cobalt, manganese, nickel and the like and composite oxides thereof. Commercial applications have demonstrated high potential and stability of these materials, but with low specific capacity (205 mAh/g). For example, lithium cobaltate (LiCoO) is the earliest commercially available positive electrode material 2 ) The theoretical specific capacity of the material is 273mAh/g, but the actual specific capacity is only about 140mAh/g, and the material also has the defects of high price and high toxicity; although lithium nickelate (LiNiO) 2 ) The specific capacity can reach 150mAh/g, which is slightly higher than LiCoO 2 However, in LiNiO 2 In the synthesis process, lithium is easy to be lost, and LiNiO meeting the standard chemical composition is synthesized 2 Is difficult; with LiCoO 2 In contrast, lithium manganate (LiMnO) 4 ) The price is low, but the theoretical specific capacity is lower (148 mAh/g), and the cycle performance is poor; lithium iron phosphate (LiFeO) 4 ) The theoretical specific capacity of the material can reach 170mAh/g, but the conductivity is poor, and the energy density is low. The theoretical specific capacity of the graphite of the negative electrode is 372mAh/g, and the actual specific capacity reaches 360mAh/g. Therefore, the specific capacity of the lithium ion battery is limited by the positive electrode material. These factors restrict the improvement of the performance of the lithium ion battery, and research and development of a novel high-performance anode material are urgently needed to meet the application of energy storage equipment. The search space for high energy density cathode materials is expanded to cation disordered lithium transition metal oxides.
Semiconductor oxide glass is considered to be an electrode material of lithium ion batteries with great potential application prospect. Prior patents have disclosed the use of composite vanadium phosphorus glasses for lithium ion battery positive electrode materials, such as V 2 O 5 -Li 3 PO 4 -CaC 2 (CN111484247A)、V 2 O 5 -LiBO 2 The lithium ion battery assembled by the positive electrode material has high specific capacity and strong battery cycle stability, and can improve the electron and ion transmission rate and inhibit the volume expansion in the charging and discharging process. But has the problems of small specific capacity, large internal resistance, low voltage, large first-turn loss rate and the like.
Disclosure of Invention
In view of this, the present invention aims to provide a selenide glass material, a preparation method thereof and an application thereof, wherein the glass material is used as a positive electrode of a lithium ion battery, such that the battery has advantages of large specific capacity, high voltage, and small first-turn loss rate.
The invention provides a selenide glass material, which comprises active substance glass powder, wherein the preparation raw material of the active substance glass powder comprises a network product selenide MSe with the mass ratio of (10-50): (30-80): (10-40) x Transition metal oxide DO y And exo-network oxides AO n ；
The x, y and n balance valences;
the MSe x Wherein M is one or more selected from Ti, si, sn, pb, P, as, sb, bi, O, S and Te;
said DO y Wherein D is selected from one or more of Fe, V, zr, sb, mo, cr, nb, ta, ni, co, cu and Mn;
said network exo-oxide AO n Wherein A is selected from one or more of Li, na, K, rb, cs, ca, sr, ba, Y, in, la, zr, th, be, mg, zn, al and Ga.
In the present invention, the network product selenide MSe x Wherein x is 1, 2 or 3; the network product selenide MSe x Preferably from SiSe 2 、SnSe、P 2 Se 5 、SeO 2 、TeSe 2 One or more of (a).
In the present invention, the transition metal oxide DO y Selected from Fe 2 O 3 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、NiO、Co 2 O 3 With Mn 2 O 7 One or more of (a).
In the present invention, the network exo-oxide AO n Selected from Li 2 O、Na 2 O、K 2 O、Rb 2 O、Cs 2 O、CaO、SrO、BaO、Y 2 O 3 、In 2 O 3 、La 2 O、ZrO 2 、ThO 2 、BeO、MgO、ZnO、Al 2 O 3 、Ga 2 O 3 、SnO、PbO、SnO 2 、Te 2 O 5 、Te 2 O 3 And Sb 2 O 3 One or more of (a).
In the present invention, the selenide glass material further includes a binder and a conductive filler;
the mass ratio of the active substance glass powder to the binder to the conductive filler is (6-10) to (2-3) to (1-2), preferably (6-8) to (2-3) to (1-2); in a specific embodiment, the mass ratio of the active material glass powder, the binder and the conductive filler is 7. In the present invention, the binder is preferably polyvinylidene fluoride; the conductive filler is preferably conductive carbon black.
In the present invention, the particle size of the active material glass powder is 400 mesh or less.
In the present invention, the selenide glass material is an active material of a positive electrode material; the molecular arrangement of the glass is random, with the molecules having statistical uniformity in space. Ideally, the physical and chemical properties (e.g., refractive index, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, electrical conductivity, etc.) of homogeneous glasses are the same in all directions. The glassy substance is generally obtained by rapidly cooling a molten body, when the glassy substance is converted from a molten state to a glassy state, the viscosity is rapidly increased in the cooling process, particles are not ready to be regularly arranged to form crystals, and latent heat of crystallization is not released, so that the glassy substance has higher internal energy than the crystalline substance, and the energy of the glassy substance is between the molten state and the crystalline state, and belongs to a metastable state. From a mechanical point of view, glass is an unstable high-energy state, and has a tendency to transform into a low-energy state, i.e., to devitrify, and therefore, is a metastable solid material. Moreover, the process of the glassy substance from a molten state to a solid state is gradual, and the change of the physical and chemical properties of the glassy substance is continuous and gradual. This is in marked contrast to the crystallization of melts, which necessarily involves the appearance of new phases, and near the crystallization temperature point, many properties are subject to abrupt changes. The glassy substance is finished in a wider temperature range from a molten state to a solid state, the viscosity of the glass melt is gradually increased along with the gradual reduction of the temperature, and finally solid glass is formed, but no new phase is formed in the process. Conversely, the process of heating the glass to become molten is also gradual.
The main raw materials for producing the glass comprise a glass forming body, a glass regulating body and a glass intermediate, and the balance is auxiliary raw materials. Wherein, the main raw materials refer to an oxide, an intermediate oxide and a network exo-oxide which are introduced into glass to form a network; the auxiliary raw materials comprise a clarifying agent, a fluxing agent, an opacifier, a coloring agent, a decoloring agent, an oxidant, a reducing agent and the like.
In the present invention, the network product selenide MSe x Transition metal oxide DO y And exo-network oxides AO n The mass ratio of (10-50) to (30-80) to (10-40), preferably (15-40): (40-70): (10-20); in a specific embodiment, the network product selenide MSe x Transition metal oxide DO y And exo-network oxides AO n The mass ratio of (A) to (B) is 20:60:20, or 15:65:20, or 20:65:15, or 25:60:15, or 40:50:10.
the invention provides a preparation method of the selenide glass material in the technical scheme, which comprises the following steps:
the network product selenide MSe x Transition metal oxide DO y With network exo-oxides AO n Mixing, heating to 500-800 ℃ in a protective atmosphere, preserving heat for 100-300 min, then continuously heating to 1000-2000 ℃, preserving heat for 10-30 min, cooling and forming, annealing, and grinding to obtain the selenide glass material.
The protective atmosphere is preferably argon.
In the invention, the annealing temperature is 200-300 ℃, and the annealing time is 200-2000 min.
The invention preferably heats to 500-800 ℃ at the speed of 5-15 ℃/min. In the present invention, the temperature is preferably raised to 500 to 800 ℃ at a rate of 5 to 15 ℃/min, more preferably to 500 to 800 ℃ at a rate of 5 to 10 ℃/min; in the present invention, the temperature is preferably raised to 600 to 800 ℃, more preferably raised to 650 to 750 ℃ for heat preservation; in the embodiment provided by the invention, the temperature is specifically raised to 700 ℃ for heat preservation; the time for heat preservation is preferably 100-200 min.
The invention preferably continuously heats up to 1000-2000 ℃ at the speed of 5-15 ℃/min, preferably continuously heats up to 1000-1500 ℃, and keeps warm; the heat preservation time is 10-30 min, preferably 10-20 min; in the present invention, the temperature is preferably raised to 1000 to 2000 ℃ at a rate of 5 to 15 ℃/min, and more preferably raised to 1000 to 2000 ℃ at a rate of 10 to 15 ℃/min.
After the heat preservation is finished, cooling and forming; in the invention, the liquid tin surface is preferably cooled and formed; spreading and flattening the molten glass on the molten tin surface to form flat upper and lower surfaces, hardening, cooling and introducing into a transition roller table.
Finally, annealing treatment is carried out to obtain glass; the temperature of the annealing treatment is preferably 200-300 ℃; the time of the annealing treatment is preferably 200 to 2000min, more preferably 200 to 1000min, and further preferably 200 to 500min; in the embodiment provided by the invention, the time of the annealing treatment is specifically 300min.
Grinding the glass to obtain active substance glass powder; the grinding is preferably carried out by a ball mill; the particle size of the active material glass powder is preferably 400 mesh or less.
If the selenide glass material also comprises a binder and a conductive filler, after active material glass powder is obtained by grinding, the active material glass powder is continuously mixed with the binder, the conductive filler and a solvent, ball milling is carried out, and the active material glass powder is coated on a current collector to obtain the selenide glass material, namely the anode material.
Mixing the active material glass powder, the binder, the conductive filler and the solvent, ball-milling, and coating on a current collector; the mass ratio of the active material glass powder, the binder and the conductive filler is preferably (6-10): (2-3): (1-2), more preferably (6-8): (2-3): (1-2); in the embodiment provided by the invention, the mass ratio of the active material glass powder to the binder to the conductive filler is specifically 7:2:1; the binder is preferably polyvinylidene fluoride; the particle size of the conductive filler is preferably 1-10 mu m; the conductive filler is preferably conductive carbon black. The solvent is preferably N-methylpyrrolidone; the current collector is preferably an aluminum foil; the thickness of the coating is 60-120 mu m.
After coating, drying, the glass positive electrode material was obtained.
The preparation method provided by the invention is simple, easy to implement and beneficial to popularization and application.
The invention provides a lithium ion battery, which comprises a positive electrode material; the positive electrode material is the selenide glass material prepared by the preparation method of the technical scheme or the selenide glass material prepared by the preparation method of the technical scheme.
The invention provides a selenide glass material, which comprises active substance glass powder, wherein the preparation raw material of the active substance glass powder comprises a network product selenide MSe with the mass ratio of (10-50): (30-80): 10-40) x Transition metal oxide DO y And network exo-oxide AO n (ii) a The x, y and n balance valences; the MSe x Wherein M is one or more selected from Ti, si, sn, pb, P, as, sb, bi, O, S and Te; said DO y Wherein D is selected from one or more of Fe, V, zr, sb, mo, cr, nb, ta, ni, co, cu and Mn; said network exo-oxide AO n Wherein A is selected from one or more of Li, na, K, rb, cs, ca, sr, ba, Y, in, la, zr, th, be, mg, zn, al and Ga. The open circuit voltage of the lithium ion battery assembled by the selenide glass material as the anode is 3.9-4.4; the first capacitance is 263-310 mAh/g; the first circulation coulomb efficiency is 91% -96%; the 100 circulation discharge capacity of the battery is 250-294 mAh/g, and the circulation efficiency is 92.3% -97.4%. The provided glass anode material has the problems of large specific capacity, high voltage, small first-turn loss rate and the like, and the preparation method has the advantages of simple process, easy implementation and contribution to popularization and application.
Drawings
FIG. 1 is an XRD spectrum of a glass powder prepared according to example 3 of the present invention;
FIG. 2 is an SEM scanning electron microscope photograph of the glass powder prepared in example 5 of the present invention.
Detailed Description
To further illustrate the present invention, the following examples are provided to describe a selenide glass material and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Based on the weight portion, 20 portions of SiSe 2 60 parts of Fe 2 O 3 20 parts of Li 2 And O, stirring and grinding uniformly, and transferring the obtained mixed raw material into an alumina crucible. Melting in a tubular heating furnace under the protection of argon, heating to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 100min; raising the temperature to 1000 ℃ at a temperature rise rate of 15 ℃/min, and preserving the heat for 30min; the mixed solution is poured onto the surface of liquid tin quickly to form the glass. Spreading and flattening the molten glass on the molten tin surface to form an upper surface and a lower surface, hardening, cooling and then leading the molten glass to a transition roller table. The rollers of the roller table rotate to pull the glass ribbon out of the tin bath and enter an annealing furnace, the temperature of the furnace body is 200 ℃, and the glass is obtained after annealing for 300min.
The glass was crushed, sufficiently ground using a ball mill, and sieved (400 mesh) to obtain a glass powder.
And (3) mixing the following components in a mass ratio of 7:2:1, mixing glass powder, a binder (polyvinylidene fluoride) and conductive carbon black (the particle size distribution is 1-10 mu m) powder, then dripping a proper amount of N-methyl pyrrolidone (accounting for 20 percent of the powder) into the mixture for ball milling, coating the obtained slurry on an aluminum foil, drying the aluminum foil, coating the aluminum foil with the thickness of 120 mu m, and then taking the aluminum foil as a positive electrode and 1mol/L LiPF 6 A CR2025 type coin cell was assembled in a glove box using ethylene carbonate/dimethyl carbonate (volume ratio 1). And testing the charge and discharge performance of the comparative sample lithium ion battery under different current densities within the voltage range of 2.0-4.2V on an electrochemical workstation.
Examples 2 to 5
Following the procedure of example 1, the different network products selenide MSe x ，VO y Transition metal oxide, AO n The type and amount of exo-network oxide added are shown in Table 1.
TABLE 1 examples 1 to 5 kinds and amounts of raw materials used for preparing glass cathode materials
| Examples | MSe x | Number of parts | VO y | Number of copies | AO n | Number of parts |
| 1 | SeO 2 | 15 | Fe 2 O 3 | 65 | Li 2 O | 20 |
| 2 | TeSe 2 | 20 | V 2 O 5 | 60 | K 2 O | 20 |
| 3 | P 2 Se 5 | 40 | Nb 2 O 5 | 50 | Te 2 O 5 | 10 |
| 4 | SeTe | 25 | Co 2 O 3 | 60 | Al 2 O 3 | 15 |
| 5 | |
20 | Mn 2 O 7 | 65 | Te 2 O 5 | 15 |
Comparative example 1
Drying the V 2 O 5 Powder with P 2 O 5 Mixing the powders at stoichiometric ratio, melting in hydrogen atmosphere to obtain 80V powder 2 O 5 ·20P 2 O 5 Glass samples. The mixture was stirred and mixed uniformly and then put into a quartz crucible. And melting the glass by adopting a tube furnace. Heating at 800 ℃ for 5min to obtain a vanadium phosphorus glass sample melt. The molten glass was poured onto an iron plate, followed by annealing in a muffle furnace at 250 ℃ for 2 hours, and then furnace-cooled. By agate grindingThe bowl grinds the prepared glass into powder with the grain diameter<20μm。
The electrode is formed by mixing an active material (vanadium phosphorus glass powder), carbon black and a Polytetrafluoroethylene (PTFE) binder in a mass ratio of 8. The weighed vanadium phosphorus glass powder and carbon black are put into an agate mortar to be ground for 30 minutes to obtain a uniform mixture. Then, polytetrafluoroethylene was added to the prepared mixture, and vigorous mixing was performed to obtain a uniform film (thickness 80 μm). The prepared cathode film was punched into a circular sheet by a circular cutter having a diameter of 8mm, and then uniformly adhered to an aluminum mesh. Then, a CR2032 coin cell (316L stainless steel, polypropylene gasket) was used as a cathode, and 1mol/L LiPF was used 6 A CR2032 type coin cell was assembled in a glove box with an electrolyte of ethylene carbonate/dimethyl carbonate (volume ratio 1), a separator of Celgard 2025, and a counter electrode of lithium sheet. And testing the charge and discharge performance of the comparative sample lithium ion battery under different current densities within the voltage range of 2.0-4.2V on an electrochemical workstation. The test data showed 270mAh g for the first time -1 Has a capacity retention rate of about 90% after 100 cycles. Furthermore, after 300 cycles at 85mA g -1 Can provide 220mAh g under high current density -1 The specific capacity of (A) corresponds to a capacity retention rate of 80%.
The performance test results of the lithium ion batteries assembled by the glass cathode materials prepared in examples 1 to 5 and comparative example 1 are shown in table 2.
Table 2 results of performance test of the glass cathode-assembled batteries prepared in examples 1 to 5 of the present invention and comparative example 1
The invention provides a selenide glass material which comprises active substance glass powder, wherein the preparation raw material of the active substance glass powder comprises a network product selenide MSe with the mass ratio of (10-50): (30-80): (10-40) x Transition metal oxide DO y And network exo-oxide AO n (ii) a The x, y and n are quantizedThe valence is balanced; the MSe x Wherein M is one or more selected from Ti, si, sn, pb, P, as, sb, bi, O, S and Te; said DO y Wherein D is selected from one or more of Fe, V, zr, sb, mo, cr, nb, ta, ni, co, cu and Mn; said network exo-oxide AO n Wherein A is selected from one or more of Li, na, K, rb, cs, ca, sr, ba, Y, in, la, zr, th, be, mg, zn, al and Ga. The open circuit voltage of the lithium ion battery assembled by the selenide glass material as the anode is 3.9-4.4V; the first capacitance is 263-310 mAh/g; the first circulation coulombic efficiency is 91-96 percent; the 100 circulation discharge capacity of the battery is 250-294 mAh/g, and the circulation efficiency is 92.3% -97.4%. The provided glass anode material has the problems of large specific capacity, high voltage, small first-turn loss rate and the like, and the preparation method has the advantages of simple process, easy implementation and contribution to popularization and application.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A selenide glass material comprises active substance glass powder, wherein the active substance glass powder is a network product selenide MSe with the mass ratio of (15-40): (50-65): 10-20) x Transition metal oxide DO y And exo-network oxides AO n Composition is carried out;
the x, y and n balance valences;
the MSe x Wherein M is one or more selected from Ti, si, sn, pb, P, as, sb, bi, O, S and Te;
said transition metal oxide DO y Selected from Fe 2 O 3 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、NiO、Co 2 O 3 With Mn 2 O 7 One or more of;
said network exo-oxide AO n Selected from Li 2 O、Na 2 O、K 2 O、Rb 2 O、Cs 2 O、CaO、SrO、BaO、Y 2 O 3 、In 2 O 3 、La 2 O、ZrO 2 、ThO 2 、BeO、MgO、Al 2 O 3 、Ga 2 O 3 、SnO、PbO、SnO 2 、Te 2 O 5 、Te 2 O 3 And Sb 2 O 3 One or more of (a).
2. The selenide glass material of claim 1, wherein the network product selenide MSe x Selected from SiSe 2 、SnSe、P 2 Se 5 、SeO 2 、TeSe 2 One or more of (a).
3. The selenide glass material of claim 1, further comprising a binder and a conductive filler;
the mass ratio of the active substance glass powder, the adhesive and the conductive filler is (6-10) to (2-3) to (1-2).
4. The selenide glass material of claim 1, wherein the active material glass powder has a particle size of 400 mesh or smaller.
5. A method for preparing the selenide glass material of any of claims 1 to 4, comprising the steps of:
the network product selenide MSe x Transition metal oxide DO y With exo-network oxides AO n Mixing, heating to 500-800 ℃ in protective atmosphere, keeping the temperature for 100-300 min, then continuing heating to 1000-2000 ℃, keeping the temperature for 10-30 min, cooling and forming, annealing, and grinding to obtain the selenide glass material.
6. The method according to claim 5, wherein the annealing temperature is 200-300 ℃ and the annealing time is 200-2000 min.
7. The method of claim 5, wherein the temperature is raised to 500-800 ℃ at a rate of 5-15 ℃/min;
the temperature is raised to 1000-2000 ℃ at the speed of 5-15 ℃/min.
8. A lithium ion battery is characterized by comprising a positive electrode material;
the positive electrode material is the selenide glass material according to any one of claims 1 to 4 or the selenide glass material prepared by the preparation method according to any one of claims 5 to 7.
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| PCT/CN2021/138254 WO2023082410A1 (en) | 2021-11-15 | 2021-12-15 | Selenide glass material, preparation method therefor, and use thereof |
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1496549B2 (en) * | 1965-09-04 | 1970-11-05 | Jenaer Glaswerk Schott & Gen, 6500 Mainz | Highly refractive, crystallization-stable, low-color, fusible optical glasses with a mean expansion coefficient alpha.10 to the power of 7 (25 to 400 degrees C) of 84 to 95 |
| DE3612727A1 (en) * | 1986-04-16 | 1987-10-29 | Bosch Gmbh Robert | HUMIDITY SENSOR |
| CN101397190A (en) * | 2007-09-27 | 2009-04-01 | 华东理工大学 | Selenium base chalcohalide glass transmitting visible light and preparation method thereof |
| US8652873B1 (en) * | 2012-08-03 | 2014-02-18 | E I Du Pont De Nemours And Company | Thick-film paste containing lead-vanadium-based oxide and its use in the manufacture of semiconductor devices |
| TWI520154B (en) * | 2012-12-28 | 2016-02-01 | 碩禾電子材料股份有限公司 | Low-temperature sinterable electroconductive paste for solar cell with high conversion efficiency |
| TWI532060B (en) * | 2013-02-08 | 2016-05-01 | 碩禾電子材料股份有限公司 | Conductive paste for solar cell and manufacturing method for electrode of solar cell |
| CN104961329B (en) * | 2015-05-13 | 2017-09-26 | 苏州市英富美欣科技有限公司 | A kind of instruments used for education glass material and preparation method thereof |
| CN108975681A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | High temperature resistant quanta point material and preparation method thereof |
| CN108623145B (en) * | 2018-06-22 | 2022-02-01 | 贵州佰博新材料科技有限公司 | Lead-free glass powder for back passivation point contact solar cell aluminum paste and preparation method thereof |
| CN110407467B (en) * | 2019-07-25 | 2021-10-29 | 西安宏星电子浆料科技股份有限公司 | Electronic glass powder for solar crystalline silicon battery front silver paste and preparation method thereof |
-
2021
- 2021-11-15 CN CN202111369439.8A patent/CN114057401B/en active Active
- 2021-12-15 WO PCT/CN2021/138254 patent/WO2023082410A1/en unknown
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| Publication number | Publication date |
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| CN114057401A (en) | 2022-02-18 |
| WO2023082410A1 (en) | 2023-05-19 |
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