CN105932285A - Preparation method for lithium battery anode material by taking metal organic frame as template - Google Patents
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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- 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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Abstract
The invention discloses a preparation method for a lithium battery anode material by taking a metal organic frame as a template. The preparation method of the lithium battery anode material comprises the steps of 1, synthesizing organic ligand 4, 4 Hopybz; 2, synthesizing a Pb-MOF material, weighing Pb(NO3)2 and the ligand 4, 4 Hopybz, dissolving the Pb(NO3)2 and the ligand 4, 4 Hopybz into solvent, carrying out heating and reacting in a reactor and cooling to a room temperature after reaction, thereby obtaining the Pb-MOF material; 3, preparing the lithium battery anode material, and heating to activate the Pb-MOF obtained in the step 2, thereby obtaining the lithium battery anode material. Compared with the prior art, the method has the advantages that a porous metal organic frame complex is synthesized, the complex is further activated, the complex is directly applied to a lithium battery as the anode material of the lithium battery, the structure and specific surface area of the metal organic frame are adjustable, and the prepared lithium battery anode material has good electrochemical performance.
Description
Technical field
The present invention relates to the application of lithium ion battery negative material, particularly relate to a kind of lithium with metal organic frame as template
The preparation method of cell negative electrode material.
Background technology
Twentieth century six the seventies, due to the outburst of first time energy crisis and constantly increases the demand of mobile energy device,
Scientists has started the research to secondary lithium battery, but up to the early 1990s, grinding in terms of lithium ion battery
Study carefully the progress of just making a breakthrough property.Lithium ion battery uses stratiform cobalt acid lithium (LiCoO2) as positive pole, graphite (C) conduct
Negative pole, and a kind of nonaqueous lithium ion conducting medium is as electrolyte.Owing to lithium ion battery only passes through Li in charge and discharge process+
Embedding in active electrode material and abjection, the shortcoming that lithium metal dissolution therefore can be overcome to be formed with reduction and dendrite arm lithium, make
Its safety strengthens, and therefore can be widely applied to current portable electronic equipment.In order to meet modern society's demand to the energy
While meet people's care to ecological environment again, scientists is constantly looking for a kind of energy cheap, eco-friendly
Source converts and stocking system, the most constantly makes one's way in life in this field.But, the performance of these equipment largely depends on
Development in material.The composition material of lithium ion battery mainly has positive electrode, negative material and electrolyte system, these compositions
The performance of material and preparation method directly influence the performance of battery, and wherein the positive and negative pole material of battery is to battery performance and cost
Affecting particularly important, therefore the research to electrode material has become as the focus of lithium ion battery material research.Lithium ion battery by
In there being the advantages such as high-energy-density, high output voltage, memory-less effect and non-environmental-pollution, more and more applied.No
Can be only applied to various portable electric appts, as electric powered motor power supply and the new forms of energy such as solar energy, wind energy
Energy storage device aspect has the biggest application prospect.The current widely used negative pole of business-like lithium ion battery is mainly graphite-like material
Material.But graphite theoretical capacity is low and has safety issue, the highest theoretical capacity, the Novel anode material that safety is good obtain more
Carry out the most concerns.Oxide cathode material has theoretical capacity height, good cycle, security performance advantages of higher, is to substitute
Graphite as the ideal material of lithium ion battery negative, but poorly conductive, irreversible capacity are big and before and after discharge and recharge change in volume big
Restrict it etc. problem and obtain actual application.
Although lithium ion battery has been widely used for the electronic equipment of daily life, but self aspect yet suffers from lacking of many
Point.In charge and discharge process, lithium ion battery electrode material easily produces structural collapse and Volumetric expansion, which results in battery
The phenomenons such as capacity attenuation and shortening in service life.In order to overcome electrode material conductivity in charge and discharge process to decline and volumetric expansion etc.
Problem, can use the material with loose structure as electrode material.
Metal organic frame is that one contains carbon source (organic ligand) and source metal (metal ion) and has periodic network knot
The porous coordination of structure, owing to it has loose structure and certain electric conductivity, has preferable storge quality to lithium ion, because of
This can be applied to lithium ion battery directly as electrode material.But so far, with MOF material directly as the lithium of electrode
There is the shortcomings such as specific capacity is less (Lin Y, Zhang Q, Zhao C, et al.An exceptionally stable in ion battery
functionalized metal–organic framework for lithium storage[J].Chemical Communications,2015,
51(4):697-699.)。
Summary of the invention
It is an object of the invention to overcome shortcoming and defect of the prior art, it is provided that a kind of lithium with metal organic frame as template
The preparation method of cell negative electrode material.
The present invention is achieved by the following technical solutions: the system of a kind of lithium cell cathode material with metal organic frame as template
Preparation Method, comprises the following steps:
(1) synthesis organic ligand 4-p-methylphenyl-pyridine-N-oxide (4,4-Hopybz)；
(2) synthesis Pb-MOF material: weigh Pb (NO3)2With part 4,4-Hopybz is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Pb-MOF material；
(3) lithium cell cathode material is prepared: by the Pb-MOF heat-activated of gained in step (2), obtain cathode of lithium battery
Material.
Relative to prior art, the present invention, by a kind of porous metals organic frame complex of synthesis, further activates, and will
It is applied in lithium battery directly as the negative material of lithium battery, described metal organic frame, and structure, specific surface area are adjustable,
The lithium cell cathode material prepared has good chemical property.When charging and discharging currents density 100mA/g, put first
Electricity specific capacity can reach 1522mAh/g, and after circulating 100 times, specific capacity maintains about 485mAh/g.At discharge and recharge electricity
During current density 500mA/g, after circulating 100 times, specific capacity maintains about 382mAh/g, and the circulation embodying it good is steady
Qualitative and high rate performance.
Further, in step (2), Pb (NO3)2It is 2:1 with the mol ratio of 4,4-Hopybz.
Further, in step (2), described solvent be volume ratio be DMF and the mixed solvent of water of 1:1.
Further, in step (1), weigh 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate and add in toluene, add
Four triphenyl phosphorus palladiums make catalyst, in nitrogen atmosphere after 80-100 ° of reaction 10-14h, spend the leaching stillness of night, and regulation pH is to acid
Property, separate out precipitation, filter to obtain white intermediate product；Dry intermediate product, add glacial acetic acid and hydrogen peroxide, after reacting by heating,
Filter to obtain 4,4-Hopybz organic ligand.
Further, in described step (1), the mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate is 1:1:1.25,
Catalyst four triphenyl phosphorus palladium is 0.00125:1 with the mol ratio of 4-bromopyridine hydrochloride.
Further, in described step (1), the volume ratio of glacial acetic acid and hydrogen peroxide is 3:2, after adding glacial acetic acid and hydrogen peroxide, and institute
Stating heating-up temperature is 80 °, and the response time is 24h.
Further, in described step (2), heating-up temperature is 80 °, and the response time is 24h.
Further, in described step (3), the Pb-MOF material in step (2) is heated under 100 ° 5h and activates,
To remove the guest molecule in framework.
Present invention also offers the preparation method of a kind of lithium battery, comprise the following steps: by lithium cell cathode material, binding agent,
Conductive black ground and mixed in proportion is uniform, with solvent furnishing pulpous state, is coated on Copper Foil, vacuum drying, cuts into slices after roll-in,
To circular electric pole piece；Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery.Described lithium cell cathode material is upper
State the lithium cell cathode material that any means mentioned prepares.
Relative to prior art, using the lithium ion battery that the lithium cell cathode material of the present invention prepares, coulombic efficiency is high,
There is high charge-discharge specific capacity, good high rate performance and cycle performance.
Further, described binding agent is Kynoar, and described conductive black is conductive acetylene white carbon black, and described solvent is N-methyl
Ketopyrrolidine；Described lithium cell cathode material, conductive black, the mass ratio of binding agent are 6:3:1.
In order to be more fully understood that and implement, describe the present invention below in conjunction with the accompanying drawings in detail.
Accompanying drawing explanation
Fig. 1 is the synthetic reaction step schematic diagram of the organic ligand of the present invention；
Fig. 2 (a) be the present invention Pb-MOF material in the coordination environment figure of metallic lead；B () is the Pb-MOF material of the present invention
In material, Pb-O is without chain figure；C () is the 3-D frame diagram of the Pb-MOF of the present invention；
Fig. 3 is the cyclic voltammetry figure of the lithium cell cathode material of the present invention；
Fig. 4 is the constant current charge-discharge curve chart of the lithium ion battery using the lithium cell cathode material of the present invention to prepare；
Fig. 5 is the cycle performance test figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare；
Fig. 6 is the high rate performance test figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare；
Fig. 7 is the ac impedance measurement figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
Detailed description of the invention
By further illustrate the present invention with the technological means reached predetermined goal of the invention and taked and technique effect thereof, below in conjunction with
Embodiment and accompanying drawing, the preparation method to a kind of lithium cell cathode material with metal organic frame as template that the present invention proposes
Detailed description of the invention illustrates, and describes in detail as follows.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template of the present invention, comprises the following steps:
(1) synthesis organic ligand 4-p-methylphenyl-pyridine-N-oxide (4,4-Hopybz): weigh 4-bromopyridine hydrochloride, 4-
Carboxybenzeneboronic acid and sodium carbonate add in toluene, add four triphenyl phosphorus palladiums and make catalyst, 80-100 ° of reaction in nitrogen atmosphere
After 10-14h, spending the leaching stillness of night, regulation pH, to acid, separate out precipitation, filters to obtain white intermediate product；Dry intermediate product,
Add glacial acetic acid and hydrogen peroxide, after reacting by heating, filter 4,4-Hopybz organic ligand.
(2) synthesis Pb-MOF material: weigh Pb (NO3)2With part 4,4-Hopybz is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Pb-MOF material.
(3) lithium cell cathode material is prepared: by the Pb-MOF heat-activated of gained in step (2), obtain cathode of lithium battery
Material.
In step of the present invention (1), the preferred 1:1:1.25 of mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate, urges
Agent four triphenyl phosphorus palladium and the preferred 0.00125:1 of mol ratio of 4-bromopyridine hydrochloride.Nitrogen atmosphere reacts under preferably 90 ° 12
h.The pH of the regulation stillness of night to acid preferably pH=1.The volume ratio of described glacial acetic acid and hydrogen peroxide is 3:2, and described heating-up temperature is
80 °, react 24h.
In step of the present invention (2), Pb (NO3)2The preferred 2:1 with the mol ratio of 4,4-Hopybz.Heating-up temperature in step (2)
Preferably 80 °, after reaction 24h, then it is reduced to room temperature.In step (2) solvent be volume ratio be the DMF of 1:1 and water mixed
Bonding solvent.
In step of the present invention (3), Pb-MOF material preferably heats 5h under 100 ° and activates, to remove the visitor in framework
Body molecule.
Present invention also offers the preparation method of a kind of lithium battery, by lithium cell cathode material, binding agent, conductive black in proportion
Ground and mixed is uniform, with solvent furnishing pulpous state, is coated on Copper Foil, vacuum drying, cuts into slices, obtain circular electric pole piece after roll-in；
Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery.Described lithium cell cathode material is that aforementioned preparation process obtains
Lithium cell cathode material.
In the present invention, described conductive black preferred conductive acetylene white carbon black, described binding agent is Kynoar.Described lithium battery
Negative material, conductive black, the mass ratio of binding agent are 6:3:1.Described solvent is N-Methyl pyrrolidone.Described vacuum drying
Condition be: in the baking oven of 60-90 °, be first dried 0.5-3h, then in 110-130 ° of dry 8-12h in vacuum drying oven.
Described diaphragm material is polyethylene.Described electrolyte is the lithium hexafluoro phosphate (LiPF containing 1mol/L6) it is electrolyte, volume ratio
Ethylene carbonate (EC): diethyl carbonate (DEC): Ethyl methyl carbonate (EMC)=1:1:1 is the electrolyte of solvent.
Embodiment 1
The preparation method of the lithium cell cathode material with metal organic frame as template is described in detail by the present embodiment.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template of the present invention, comprises the steps:
(1) synthesis organic ligand 4-p-methylphenyl-pyridine-N-oxide (4,4-Hopybz)
Referring to Fig. 1, it is the synthetic reaction step schematic diagram of the organic ligand in the present invention.Weigh the 4-of 8mmol respectively
The natrium carbonicum calcinatum of bromopyridine hydrochloride, the 4-Carboxybenzeneboronic acid of 8mmol and 10mmol joins in toluene solution, adds
The four triphenyl phosphorus palladiums of 0.01mmol, under catalyst four triphenyl phosphorus palladium effect and in nitrogen atmosphere, react 12h in 90 °
After, spend the leaching stillness of night, add dilute hydrochloric acid regulation pH=1, filter to obtain white intermediate product.Intermediate product is dried, adds 30mL
Glacial acetic acid and 20mL hydrogen peroxide, 80 ° of reaction 24h, it is filtrated to get 4,4-Hopybz organic ligand.
(2) synthesis Pb-MOF material
Weigh the Pb (NO of 0.1mmol3)2H with 0.05mmol2PYBIA is dissolved in the DMF that volume ratio is 1:1 of 6mL
And H2After in O mixed solvent, in the reactor that liner is politef material, after 80 ° of reacting by heating 24h, it is down to
Room temperature, obtains Pb-MOF material.
(3) lithium cell cathode material is prepared
At 100 DEG C, heat 5h with the Pb-MOF obtained in step (2), remove guest molecule, make Pb-MOF activate,
Obtain lithium cell cathode material.
The present embodiment additionally provides a kind of method using lithium cell cathode material to prepare lithium ion battery.Concrete, by lithium battery
Negative material, conductive black, the mass ratio of binding agent are 6:3:1 mixing, are solvent furnishing pulpous state with N-Methyl pyrrolidone,
It is coated on Copper Foil, in the baking oven of 80 °, is first dried 1h, then in 120 ° of dry 10h in vacuum drying oven.Cut into slices after roll-in,
Obtain circular electric pole piece.By electrode slice, polyethylene diagrams material, electrolyte is the LiPF of 1mol/L6, solvent be that volume ratio is
The electrolyte of the mixed solution of EC, DEC and EMC of 1:1:1 is assembled into lithium ion battery.The most described lithium from
Sub-battery be model be the button cell of 2032, but be not limited to this.
Relative to prior art, the present invention, by a kind of porous metals organic frame complex of synthesis, further activates, and will
It is applied in lithium battery directly as the negative material of lithium battery, described metal organic frame, and structure, specific surface area are adjustable,
The lithium cell cathode material prepared has good chemical property.
Effect example
Please refer to Fig. 2, (a) be the present invention Pb-MOF material in the coordination environment figure of metallic lead；B () is the present invention
Pb-MOF material in Pb-O without chain figure；C () is the 3-D frame diagram of the Pb-MOF of the present invention.From Fig. 2 (a)
Understanding, in Pb-MOF, the ligancy of metallic lead is 7.Fig. 2 (c) show Pb-MOF material exist the biggest hole and in
Reveal regularly arranged.
Referring to Fig. 3, it is the cyclic voltammetry figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
It can be seen that there is the oxidoreduction peak of in the first run is tested, and this peak disappears in second and third is taken turns, and this returns
Tie in an irreversible process, i.e. form SEI film at electrode surface.
Referring to Fig. 4, it is the constant current charge-discharge curve chart of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
It can be seen that the charge and discharge platform of lithium ion battery that described lithium cell cathode material prepares is at below 1V, there is ratio
Relatively low charge and discharge platform, illustrates that the lithium cell cathode material obtained by preparation method of the present invention has good electricity
Chemical property.
Referring to Fig. 5, it is the cycle performance test figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
When the lithium cell cathode material of the present invention is used for preparing lithium ion battery, show good charge-discharge performance, in electric current density be
During 100mA/g, electric discharge first can reach 1522mAh/g, and through the circulation of 100 discharge and recharges, its specific capacity can be stablized
About 486mAh/g, its coulombic efficiency is higher, shows good chemical property.
Referring to Fig. 6, it is the high rate performance test figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
It can be seen that when charging and discharging currents density 100mA/g, after circulating 100 times, specific capacity maintains about 485mAh/g.
When charging and discharging currents density 500mA/g, after circulating 100 times, specific capacity maintains about 382mAh/g, does not decay too
Many, embody the high rate performance that material is good.
Referring to Fig. 7, it is the ac impedance measurement figure of the lithium ion battery using the lithium cell cathode material of the present invention to prepare.
Before circulation, the impedance of electrode material is relatively big, along with the formation of SEI film after circulation, and negative material and diaphragm material, diaphragm material
And the interfacial resistance between positive electrode reduces.
Relative to prior art, the present invention, by a kind of porous metals organic frame complex of synthesis, further activates, and will
It is applied in lithium battery directly as the negative material of lithium battery.When charging and discharging currents density 100mA/g, discharge ratio first
Capacity can reach 1522mAh/g, and after circulating 100 times, specific capacity maintains about 485mAh/g.Close at charging and discharging currents
During degree 500mA/g, after circulating 100 times, specific capacity maintains about 382mAh/g, embodies its good cyclical stability
And high rate performance.Further, metal organic frame of the present invention, structure, specific surface area are adjustable, the lithium battery prepared
Negative material has good chemical property.
The invention is not limited in above-mentioned embodiment, if to the various changes of the present invention or deformation without departing from the spirit of the present invention
And scope, if within the scope of these are changed and deform claim and the equivalent technologies belonging to the present invention, then the present invention is also intended to
Comprise these to change and deformation.
Claims (10)
1. the preparation method of the lithium cell cathode material with metal organic frame as template, it is characterised in that: comprise the following steps:
(1) synthesis organic ligand 4-p-methylphenyl-pyridine-N-oxide (4,4-Hopybz)；
(2) synthesis Pb-MOF material: weigh Pb (NO3)2With part 4,4-Hopybz is dissolved in solvent, in reactor
Reacting by heating, reaction is down to room temperature after terminating, is obtained Pb-MOF material；
(3) lithium cell cathode material is prepared: by the Pb-MOF heat-activated of gained in step (2), obtain cathode of lithium battery
Material.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 1, it is special
Levy and be: in step (2), Pb (NO3)2It is 2:1 with the mol ratio of 4,4-Hopybz.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 1 and 2,
It is characterized in that: in step (2), described solvent be volume ratio be DMF and the mixed solvent of water of 1:1.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 1, it is special
Levy and be: in step (1), weigh 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate and add in toluene, add
Four triphenyl phosphorus palladiums make catalyst, in nitrogen atmosphere after 80-100 ° of reaction 10-14h, spend the leaching stillness of night, and regulation pH is extremely
Acidity, separates out precipitation, filters to obtain white intermediate product；Drying intermediate product, add glacial acetic acid and hydrogen peroxide, heating is anti-
Ying Hou, filter 4,4-Hopybz organic ligand.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 4, it is special
Levying and be: in described step (1), the mol ratio of 4-bromopyridine hydrochloride, 4-Carboxybenzeneboronic acid and sodium carbonate is 1:1:1.25,
Catalyst four triphenyl phosphorus palladium is 0.00125:1 with the mol ratio of 4-bromopyridine hydrochloride.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 5, it is special
Levy and be: in described step (1), the volume ratio of glacial acetic acid and hydrogen peroxide is 3:2, after adding glacial acetic acid and hydrogen peroxide, institute
Stating heating-up temperature is 80 °, and the response time is 24h.
The preparation method of a kind of lithium cell cathode material with metal organic frame as template the most according to claim 3, it is special
Levying and be: in described step (2), heating-up temperature is 80 °, the response time is 24h.
8. according to a kind of cathode of lithium battery with metal organic frame as template described in any claim in claim 1-2 or 4-7
The preparation method of material, it is characterised in that: in described step (3), by the Pb-MOF material in step (2) at 100 °
Lower heating 5h activates, to remove the guest molecule in framework.
9. the preparation method of a lithium battery, it is characterised in that: comprise the following steps: by lithium cell cathode material, binding agent, lead
Electricity white carbon black ground and mixed in proportion is uniform, with solvent furnishing pulpous state, is coated on Copper Foil, and vacuum drying is cut into slices after roll-in,
Obtain circular electric pole piece；Electrode slice, diaphragm material, electrolyte are assembled into lithium ion battery；Described lithium ion battery anode material
The porous carbon materials that material prepares for preparation method described in any claim in claim 1-8.
The preparation method of lithium battery the most according to claim 9, it is characterised in that: described binding agent is Kynoar, institute
Stating conductive black is conductive acetylene white carbon black, and described solvent is N-Methyl pyrrolidone；Described lithium cell cathode material, conduction
White carbon black, the mass ratio of binding agent are 6:3:1.
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| CN107492637A (en) * | 2017-07-18 | 2017-12-19 | 华南师范大学 | A kind of porous carbon blended metal oxide and lithium ion battery prepared therefrom |
| CN107658449A (en) * | 2017-09-17 | 2018-02-02 | 北京工业大学 | A kind of preparation method of electrode material of lithium battery |
| KR101930162B1 (en) | 2017-05-26 | 2018-12-17 | 동국대학교 산학협력단 | Sodium-Based Anode Active Material and Secondary Battery Having the Same |
| CN109686981A (en) * | 2018-12-25 | 2019-04-26 | 河南电池研究院有限公司 | A kind of compound binding agent and preparation method thereof applied to lithium-sulfur cell |
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| CN113991057A (en) * | 2021-11-11 | 2022-01-28 | 合肥国轩高科动力能源有限公司 | Lithium battery negative electrode material and preparation method of lithium battery negative electrode material applied to lithium battery |
| CN115594229A (en) * | 2022-10-18 | 2023-01-13 | 香港理工大学（Hk） | Nano high-entropy oxide material, preparation method thereof and lithium-sulfur battery positive electrode material |
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| CN113991057A (en) * | 2021-11-11 | 2022-01-28 | 合肥国轩高科动力能源有限公司 | Lithium battery negative electrode material and preparation method of lithium battery negative electrode material applied to lithium battery |
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