CN104993116A - Preparation method of self-assembled lithium ion battery positive material V2O5 - Google Patents

Preparation method of self-assembled lithium ion battery positive material V2O5 Download PDF

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CN104993116A
CN104993116A CN201510254129.XA CN201510254129A CN104993116A CN 104993116 A CN104993116 A CN 104993116A CN 201510254129 A CN201510254129 A CN 201510254129A CN 104993116 A CN104993116 A CN 104993116A
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lithium
ion batteries
anode material
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CN104993116B (en
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黄剑锋
乔晓宁
许占位
欧阳海波
李嘉胤
孔新刚
卢静
王瑞谊
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Shenzhen Zhongyuda Machinery Co ltd
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Shaanxi University of Science and Technology
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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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A preparation method of a self-assembled lithium ion battery positive material V2O5 comprises the following steps: dissolving ammonium metavanadate and oxalic acid in deionized water, adding a certain amount of diethylenetriamine or ethylene diamine, carrying out ultrasonic treatment to prepare a suspension, centrifuging the suspension, drying to obtain a precursor, and carrying out heat treatment on the precursor to obtain the lithium ion battery positive material V2O5. Compared with 600DEG C calcining and solvothermal methods in the prior art, the method allows heat treatment to be carried out at 250-450DEG C, and has the advantages of mild reaction conditions, small energy consumption, easy realization, large-scale production facilitating, and also has the advantages of simple process, low cost, easy control of the process, and environmental protection due to no use of a template. The initial discharge specific capacity of V2O5 prepared in the invention is 231mAh.g<-1>, and the discharge specific capacity after 50 cycles is 219mAh.g<-1>, so the capacity retention rate can reach 95% and is high.

Description

A kind of self assembly anode material for lithium-ion batteries V 2o 5preparation method
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, be specifically related to a kind of self assembly anode material for lithium-ion batteries V 2o 5preparation method.
Background technology
Along with the development of science and technology, the demand of people to energy storage material is increasing.Lithium ion battery, because of advantages such as its high-energy-density, stable cycle performance, memory-less effect and environmental protections, has been widely used in all kinds of pocket electronic device, the fields such as hybrid vehicle and electrical network energy storage.For battery, its energy density depends primarily on positive electrode, and the actual specific capacity of the positive electrode of current main flow is all at 170mAh g -1left and right.Therefore, the anode material for lithium-ion batteries that R and D have a more height ratio capacity has important theory significance and using value.
V 2o 5as a kind of intercalation materials of li ions of layer structure.In theory, as embedding two Li +time, theoretical specific capacity can reach 294mAh g -1.But, V 2o 5cyclical stability poor, this restrict V 2o 5further developing as battery material.At present, main solution is that material is carried out nanometer, prepares the V with self-assembled structures 2o 5, improve its chemical property.
At present, preparation has the anode material for lithium-ion batteries V of self-assembled structures 2o 5the method of powder mainly contains hydro thermal method.Liqiang Mai [Liqiang Mai, Qinyou An, Qiulong Wei, et al.Nanoflakes-Assembles Three-Dimensional Hollow-Porous V 2o 5as Lithium storagecathodes with High-rate Capacity [J] .Small.2014,10:3232 – 3237.] etc. be template with carbosphere, with NH 4vO 3together add in ethylene glycol solvent, by water-bath 80 DEG C, reaction 2.5h arrives homogeneous solution; Under 180 DEG C of hydrothermal conditions, react 12h, obtain product; The hollow porous micro sphere of nanometer sheet composition is finally prepared at 450 DEG C of calcining 2h.At 2.0-4.0V, 100mA g -1under condition, first discharge specific capacity is 283mAh g -1, circulation 60 circle capability retention is 77%.Qi Yue [Qi Yue, Hao Jiang, et al.Mesoporoussingle-crystalline V 2o 5nanorods assembled into hollow microspheres as cathodematerials for high-rate and long-life lithium-ion batteries [J] .ChemComn.2014,50:13362 – 13365.] etc. with NH 4vO 3for raw material, ethylene glycol is solvent, using polyvinylpyrrolidone (PVP) as surfactant, and adds KBr and stirs, under 200 DEG C of hydrothermal conditions, react 12h, obtain nanometer rods self assembly through 400 DEG C of heat treatment 2h and form the V with hollow microsphere structure 2o 5.At 2.0-4.0V, 147mA g -1under condition, first discharge specific capacity reaches 145.8mAh g -1, after 200 circle circulations, capacity remains on 128mAh g -1.Above method all adopts solvent-thermal method, prepares the V with self-assembled structures 2o 5.But all have employed template, and when water-heat process produces, HTHP is higher to equipment requirement, the output of product is less and repeatability is not high, is unfavorable for large-scale industrial production.
Summary of the invention
The object of the present invention is to provide that a kind of technical process is simple, energy consumption is low, can be mass-produced has self assembly anode material for lithium-ion batteries V 2o 5preparation method, the reaction temperature of the method is low, and productive rate is high, and reproducible, and obtained anode material for lithium-ion batteries V 2o 5powder chemical composition is homogeneous, good cycling stability.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of self assembly anode material for lithium-ion batteries V 2o 5preparation method, comprise the following steps:
1) ammonium metavanadate is dissolved in deionized water, stirs and obtain 0.10 ~ 0.30molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, after stirring, obtain blackish green solution, then in blackish green solution, add diethylenetriamine or ethylenediamine, mix and obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.01mol:4mL or NH with the ratio of diethylenetriamine 4vO 3be 0.01mol:4mL with the ratio of ethylenediamine;
3) pH value of B solution is regulated to be after 0.5 ~ 4.0, ultrasonic under 800 ~ 1500W, obtain suspension;
4) suspension is carried out centrifugation and obtain powder product, then by dry after powder product deionized water and absolute ethyl alcohol cyclic washing, obtain presoma;
5) presoma is heated 1 ~ 3h at 250 DEG C ~ 450 DEG C, obtain self assembly anode material for lithium-ion batteries V 2o 5.
Described step 1) in ammonium metavanadate for analyze pure.
Described step 2) in stir time be 1 ~ 2h.
Described step 3) in pH value be employing 1 ~ 3molL -1hydrochloric acid carries out regulating.
Described step 3) in the ultrasonic time be 1 ~ 4h.
Described step 4) in drying carry out in vacuum drying chamber.
Described step 4) in dry temperature be 60 ~ 80 DEG C, drying time is 6 ~ 12h.
Described step 5) in heating carry out in Muffle furnace.
Compared with prior art, the useful effect that has of the present invention:
The present invention by by ammonium metavanadate and dissolving oxalic acid in deionized water, then a certain amount of diethylenetriamine or ethylenediamine is added, obtained suspension under 800-1500W ultrasound condition, suspension is centrifugal, drying obtains presoma again, again presoma is heat-treated, obtain anode material for lithium-ion batteries V 2o 5to calcine with 600 DEG C of the prior art and compared with solvent-thermal method, heat treatment at 250 DEG C ~ 450 DEG C in the present invention, visible reaction condition of the present invention is gentle; energy consumption is less; be easy to realize, be beneficial to large-scale production, and do not use template due to the present invention; so preparation process is simple; cost is lower, and process is easily controlled, environmentally friendly.
V obtained by the present invention 2o 550 ~ 80nm is about by diameter, length is about the nanometer rods self assembly formation of 1 μm, and be coralloid loose porous road structure, chemical composition is homogeneous, purity is higher, has larger specific area, not only effectively can increase the contact area with electrolyte, thus promote the transmission of lithium ion, improve the chemical property of material.
In addition, the V that obtains of the present invention 2o 5open structure also for the embedding of lithium ion provides more avtive spot, improve the specific capacity of electrode material; Meanwhile, the V of self-assembled nano structures 2o 5in lithium ion charge and discharge process, the volumetric expansion can effectively alleviated Lithium-ion embeding He deviate to cause, is conducive to the structural stability improving material, and then improves the useful life of battery.
The V that the present invention obtains 2o 5first discharge specific capacity is 231mAh g -1, through 50 circle circulation 219mAhg -1, capability retention can reach 95%, and capability retention is high.In addition, the V that obtains of the present invention 2o 5also can be used for the fields such as catalyst, ultracapacitor and photocatalysis, be with a wide range of applications and research potential.
Accompanying drawing explanation
Fig. 1 is anode material for lithium-ion batteries V prepared by the embodiment of the present invention 1 2o 5x-ray diffraction (XRD) collection of illustrative plates of crystallite.
Anode material for lithium-ion batteries V prepared by Fig. 2 embodiment of the present invention 2 2o 5eSEM (SEM) photo (multiplication factor: 20,000 times) of crystallite.
Fig. 3 is anode material for lithium-ion batteries V prepared by the embodiment of the present invention 2 2o 5eSEM (SEM) photo (multiplication factor: 100,000 times) of crystallite
Fig. 4 is anode material for lithium-ion batteries V prepared by the embodiment of the present invention 4 2o 5crystallite between 1.8V ~ 4.0V voltage, 100mA g -1under current density condition, circulate the charge-discharge performance figure of 50 times.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
V prepared by the present invention 2o 5nano material is dispersed in the homogeneous mixture obtaining pasty state in 1-METHYLPYRROLIDONE (NMP) solution after mixing according to the mass ratio of 8:1:1 with acetylene black, polyvinylidene fluoride (PVDF) binding agent; Be coated on aluminium foil, and as the positive pole of battery after 80 DEG C of vacuumize 12h.Being negative pole with metal lithium sheet, take polypropylene screen as barrier film, using lithium-ion battery electrolytes (manufacturer: Shenzhen Xinzhoubang Technology Co., Ltd) as electrolyte, in the glove box of filling full high-purity argon gas, is assembled into button cell.It is on the high precision test macro of CT-3008W-5V10mA-S4 that the charging and discharging of battery tests Shenzhen product model under room temperature.The voltage range of test is that (reference is in Li/Li for 4.0 ~ 1.8V +).
Be described below by specific embodiment.
Embodiment 1
1) by analytically pure for 0.01mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.10molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 1h and obtain blackish green solution, then add the diethylenetriamine of 4mL, mix under magnetic agitation condition, obtain solution, be designated as B solution;
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 4.0, and under 800W, ultrasonic 1h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 60 DEG C dry 6h, obtain presoma;
5) presoma is placed in Muffle furnace, under 250 DEG C of conditions, heats 3h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
As can be seen from Figure 1, the product that prepared by the present embodiment is the V of pure phase 2o 5.
Embodiment 2
1) by analytically pure for 0.015mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.15molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 1.5h and obtain blackish green solution, then add diethylenetriamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.015mol:6mL with the ratio of diethylenetriamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 3.5, and under 900W, ultrasonic 1.5h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 70 DEG C dry 8h, obtain presoma;
5) presoma is placed in Muffle furnace, at 300 DEG C, heats 2.5h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
As can be seen from Figures 2 and 3, the V for preparing of the present embodiment 2o 5the coralliform multi-pore channel structure that the nanometer rods that to have by diameter be 50 ~ 80nm forms.
Embodiment 3
1) by analytically pure for 0.02mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.20molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 2h and obtain blackish green solution, then add diethylenetriamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.02mol:8mL with the ratio of diethylenetriamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 3.0, and under 1000W, ultrasonic 2h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 70 DEG C dry 10h, obtain presoma;
5) presoma is placed in Muffle furnace, at 350 DEG C, heats 1.5h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
Embodiment 4
1) by analytically pure for 0.025mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.25molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 2h and obtain blackish green solution, then add diethylenetriamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.025mol:10mL with the ratio of diethylenetriamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 2.0, and under 1200W, ultrasonic 3h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 80 DEG C dry 12h, obtain presoma;
5) presoma is placed in Muffle furnace, at 400 DEG C, heats 1.5h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
As can be seen from Figure 4, the self assembly coralliform anode material for lithium-ion batteries V that the present embodiment is obtained 2o 5first discharge specific capacity is 231mAh g -1, through 50 circle circulation 219mAh g -1, capability retention can reach 95%.
Embodiment 5
1) by analytically pure for 0.03mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.30molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 2h and obtain blackish green solution, then add diethylenetriamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.03mol:12mL with the ratio of diethylenetriamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 0.5, and under 1500W, ultrasonic 4h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 80 DEG C dry 12h, obtain presoma;
5) presoma is placed in Muffle furnace, at 450 DEG C, heats 1h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
Embodiment 6
1) by analytically pure for 0.03mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.3molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 2h and obtain blackish green solution, then add ethylenediamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.03mol:12mL with the ratio of ethylenediamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 0.5, and under 1500W, ultrasonic 4h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 80 DEG C dry 12h, obtain presoma;
5) presoma is placed in Muffle furnace, at 450 DEG C, heats 1h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.
Embodiment 7
1) by analytically pure for 0.01mol ammonium metavanadate (NH 4vO 3) be dissolved in the deionized water of 100mL, stir and obtain 0.10molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, stir 2h and obtain blackish green solution, then add ethylenediamine, mix under magnetic agitation condition, obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.01mol:4mL with the ratio of ethylenediamine.
3) 2molL is used -1hydrochloric acid regulates the pH value of B solution to be after 0.5, and under 1500W, ultrasonic 4h, obtains suspension;
4) suspension is carried out centrifugation and obtains powder product, then powder product is used deionized water and absolute ethyl alcohol cyclic washing respectively, then in vacuum drying chamber at 80 DEG C dry 12h, obtain presoma;
5) presoma is placed in Muffle furnace, at 450 DEG C, heats 1h, obtain self assembly coralliform anode material for lithium-ion batteries V 2o 5.

Claims (8)

1. a self assembly anode material for lithium-ion batteries V 2o 5preparation method, it is characterized in that, comprise the following steps:
1) ammonium metavanadate is dissolved in deionized water, stirs and obtain 0.10 ~ 0.30molL -1nH 4vO 3solution, is designated as solution A;
2) according to mol ratio ammonium metavanadate: oxalic acid=1:1, in solution A, add oxalic acid, after stirring, obtain blackish green solution, then in blackish green solution, add diethylenetriamine or ethylenediamine, mix and obtain solution, be designated as B solution; Wherein, NH 4vO 3be 0.01mol:4mL or NH with the ratio of diethylenetriamine 4vO 3be 0.01mol:4mL with the ratio of ethylenediamine;
3) pH value of B solution is regulated to be after 0.5 ~ 4.0, ultrasonic under 800 ~ 1500W, obtain suspension;
4) suspension is carried out centrifugation and obtain powder product, then by dry after powder product deionized water and absolute ethyl alcohol cyclic washing, obtain presoma;
5) presoma is heated 1 ~ 3h at 250 DEG C ~ 450 DEG C, obtain self assembly anode material for lithium-ion batteries V 2o 5.
2. self assembly anode material for lithium-ion batteries V according to claim 1 2o 5preparation method, it is characterized in that, described step 1) in ammonium metavanadate for analyze pure.
3. self assembly anode material for lithium-ion batteries V according to claim 1 2o 5preparation method, it is characterized in that, described step 2) in stir time be 1 ~ 2h.
4. self assembly anode material for lithium-ion batteries V according to claim 1 2o 5preparation method, it is characterized in that, described step 3) in pH value be employing 1 ~ 3molL -1hydrochloric acid carries out regulating.
5. the self assembly anode material for lithium-ion batteries V according to claim 1 or 4 2o 5preparation method, it is characterized in that, described step 3) in the ultrasonic time be 1 ~ 4h.
6. self assembly anode material for lithium-ion batteries V according to claim 1 2o 5preparation method, it is characterized in that, described step 4) in drying carry out in vacuum drying chamber.
7. the self assembly anode material for lithium-ion batteries V according to claim 1 or 6 2o 5preparation method, it is characterized in that, described step 4) in dry temperature be 60 ~ 80 DEG C, drying time is 6 ~ 12h.
8. self assembly anode material for lithium-ion batteries V according to claim 1 2o 5preparation method, it is characterized in that, described step 5) in heating carry out in Muffle furnace.
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CN105762349A (en) * 2016-01-29 2016-07-13 中国科学院过程工程研究所 Multi-shell metal oxide hollow sphere synthesized based on anion adsorption and preparation method as well as application thereof
CN105762349B (en) * 2016-01-29 2018-06-12 中国科学院过程工程研究所 More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application
CN107365256A (en) * 2017-08-09 2017-11-21 龙岩学院 The three core vanadium clusters and its synthetic method of a kind of propeller configurations
CN107827155A (en) * 2017-10-31 2018-03-23 攀钢集团攀枝花钢铁研究院有限公司 A kind of nanometer V2O5Preparation method
CN111509225A (en) * 2020-04-22 2020-08-07 中南大学 Preparation method of vanadium-based positive electrode material of zinc ion battery, product and application thereof
CN111509225B (en) * 2020-04-22 2022-06-07 中南大学 Preparation method of vanadium-based positive electrode material of zinc ion battery, product and application thereof
CN113371758A (en) * 2021-07-01 2021-09-10 陕西理工大学 Short rod self-assembly coralliform Cu11O2(VO4)6Preparation method of flower ball
CN113371758B (en) * 2021-07-01 2023-02-17 陕西理工大学 Short rod self-assembly coralliform Cu 11 O 2 (VO 4 ) 6 Preparation method of flower ball
CN113929072A (en) * 2021-10-14 2022-01-14 深圳大学 LFP @ VSe2 composite positive electrode material and preparation method thereof
CN113929072B (en) * 2021-10-14 2023-04-04 深圳大学 LFP @ VSe2 composite positive electrode material and preparation method thereof
RU2780802C1 (en) * 2021-11-10 2022-10-04 Государственное бюджетное образовательное учреждение высшего образования Московской области «Университет «Дубна» (государственный университет «Дубна») Positive electrode and primary lithium chemical current source containing it

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