CN108682840A - Nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application - Google Patents
Nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application Download PDFInfo
- Publication number
- CN108682840A CN108682840A CN201810587675.9A CN201810587675A CN108682840A CN 108682840 A CN108682840 A CN 108682840A CN 201810587675 A CN201810587675 A CN 201810587675A CN 108682840 A CN108682840 A CN 108682840A
- Authority
- CN
- China
- Prior art keywords
- nanometer
- powder
- preparation
- oxide
- ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010949 copper Substances 0.000 claims abstract description 62
- 239000011701 zinc Substances 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006230 acetylene black Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000000713 high-energy ball milling Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 238000003836 solid-state method Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 10
- 238000003795 desorption Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241000339446 Lamprotula scripta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003576 Sr0.5Ba0.5 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application.By mixing magnesia, cobalt oxide, nickel oxide, copper oxide and Zinc oxide powder according to equimolar metallic atom stoichiometric ratio, by ball milling, cold pressing clamp dog, again ball milling, nanometer (Mg is obtained0.2Co0.2Ni0.2Cu0.2Zn0.2)O.Utilize the nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder press constituent mass percentage:(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders 70%, acetylene black 20%, lithium ion battery negative material is made in binder 10%.The present invention uses high temperature solid-state method one-step synthesis (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O block materials, then the nanometer (Mg of structure in the form of sheets is obtained by high-energy ball milling method0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder, operating procedure is simple, at low cost, pollution-free.The present invention utilizes the nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) lithium ion battery negative material prepared by O, higher specific capacity can be kept under the charging and discharging currents density of 100mA/g, and there is excellent cyclical stability.
Description
Technical field
The invention belongs to nano material preparation and new energy devices fields, and in particular to a kind of nanometer
(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application.
Background technology
Lithium ion battery becomes the preferable battery system of current comprehensive performance because it is with excellent characteristic, has become
Current and following important one of the new energy.As its application field is from civilian information industry (mobile phone, laptop
Equal portable electronic devices) further expanding to energy traffic (electric vehicle etc.), then it is military to national defense and military fields are used as
Indispensable important energy source is equipped, this all proposes the charging and discharging capacity of lithium ion battery and fast charging and discharging ability
Higher requirement.Negative material is one of the key factor for determining lithium ion battery comprehensive performance quality.It is negative to lithium ion battery
The research of pole material is concentrated mainly on carbon material, silicon materials and transition metal oxide material.Currently, commercialization carbon negative pole material
Existing main problem is:Actual specific capacity low (about 300mAh/g~330mAh/g, theoretical specific capacity 372mAh/g), head
Big, rate charge-discharge poor performance of secondary irreversible loss etc., and intercalation potential is low, and graphite surface may draw in charge and discharge process
The deposition of metal Li dendrite is played, there are some potential safety problemss.Main problem existing for silicium cathode material is in charge and discharge process
In electrode material there is the volume expansion more than 400%, thus electrode material easily pulverization leads to its charging and discharging capacity
It is rapid to decline.Therefore, try to explore the new type lithium ion battery that charging and discharging capacity is high, capacity attenuation rate is small, has a safety feature
Negative material system, it has also become the hot spot of colleague's research both at home and abroad.In available negative material, transition metal oxide material
It occupies greatly, is the negative material system having wide application prospects.
People's early stage studies transition metal oxide as storage lithium titanate cathode material, such as Fe2O3、TiO2、WO2With
MoO2Deng.But there are a certain amount of irreversible capacity losses after being recycled because of first charge-discharge so that was once absorbed in their research
Low ebb.2000, J.M.Tarascon etc. existed《Nature》On magazine to the transition metal oxide MO of nanoscale (M=Co,
Fe, Ni or Cu) it is reported as lithium ion battery negative material.It was found that its electrochemistry of the type oxide of nanoscale
Conventional material can be differed markedly from, reversible specific capacity is protected between 600mAh/g~800mAh/g, and with higher capacity
Holdup.This shows that nano-metal-oxide in the lithium storage content for improving negative material, improves the cycle life side of lithium ion battery
Face shows certain advantage.
Material is a kind of new ceramic material occurred recent years, and there is Determination of multiple metal elements uniformly to divide in atomic level
Scattered feature.And material has sluggish diffusion effect, thus its microstructure is stablized.At present to research be concentrated mainly on it is following
Several aspects:(1) fluorite type (Hf0.25Zr0.25Ce0.25Y0.25)O2-δSynthetic method, such as document [Joshua G., Mojtaba
S.,Kenneth V.and Jian L.J.Eur.Ceram.Soc.2018,38,3578.];(2) a series of Ca-Ti ore types
(Sr0.5Ba0.5)(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3Preparation, such as document [Sicong J., Tao H., Joshua G.and
Jian L.Scripta Materialia,2018,142,116.];(3) phase stability in material and distortion of lattice, such as document
[G.Anand,Alex P.Wynn,Christopher M.Handley and Colin L.Freeman,Acta
Materialia,2018,146,119.];(4) five yuan of synthesis and method for manufacturing thin film, as document [Rost, C.M.,
Sachet,E.,Borman,T.,Moballegh,A.,Dickey,E.C.,Hou,D.,Jones,J.L.,Curtarolo,S.&
Maria,J.-P.Nature Comm.2015,6,8485];(5)
The abnormal dielectric constant phenomenon of material, as document [B é rardan, D., Franger, S., Dragoe, D., Meena,
A.K.&Dragoe,N.Phys.Status Solidi RRL 2016,10,328.];(6)
Adulterate Li+、Na+、K+、Ga3+Have ultrafast ionic conductivity, as document [B é rardan, D., Franger, S.,
Meena,A.&Dragoe,N.J.Mater.Chem.A 2016,4,9536.];(7)Cu2+The content of ion compares distortion of lattice
It influences, such as document [Berardan, D.;Meena,A.K.;Franger,S.;Herrero,C.;Dragoe,
N.J.Alloy.Comp.2017,704,693.];(8) crystal structure of the fine absorption spectra research of synchrotron radiation X-ray is used, such as
Document [Rost, C.M.;Rak,Z.;Brenner,D.W.;Maria,J.P.J.Am.Ceram.Soc.2017,100,2732.];
(9) ternary to seven yuan high entropy rare earth oxide synthetic method, such as document [Djenadic, R.;Sarkar,A.;Clemens,
O.;Loho,C.;Botros,M.;Chakravadhanula,V.S.K.;Kubel,C.;Bhattacharya,S.S.;
Gandhif,A.S.;Hahn,H.Mater.Res.Lett.,2017,5,102.].
In order to enable Oxide as Anode Material for Lithium Ion Batteries realize the marketization requirement, reduce the cost of raw material and
Simplify its preparation process, solve the shortcomings of INVENTIONConventional metal-oxide negative material charging and discharging capacity is relatively low, cyclical stability is poor,
It is the current technical issues that need to address.
Invention content
In order to solve the above problem of the existing technology, the present invention provides a kind of nanometers
(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application.
In a first aspect, the present invention provides a kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method, including with
Lower step:
Step (1):First magnesia of the purity higher than 99.99%, oxidation are weighed by equimolar metallic atom stoichiometric ratio
Cobalt, nickel oxide, copper oxide and Zinc oxide powder, and it is packed into ZrO2In ball grinder;Ratio of grinding media to material 10 is pressed again:1-20:1 is packed into ZrO2Mill
Ball;
Step (2):The ball grinder is sealed, and is vacuumized, inert gas is then charged with;
Step (3):The ball grinder is installed on high energy ball mill, and covers outer cover, is turned in 1000-2000r/min
Speed lower continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
Step (4):The obtained composite powder is packed into mold, then with tablet press machine by its cold moudling, be made 1cm ×
The green compact of 1cm × 0.5cm;
Step (5):By the green compact be placed in Muffle furnace high temperature calcining, after be slowly cooled to room temperature, obtain
(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
Step (6):(the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks are continuous in ethyl alcohol-isopropyl alcohol mixed solvent
High-energy ball milling 60-70 hours obtains nanometer (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder.
With reference to first aspect, in the first possible embodiment of first aspect, the cobalt oxide in step (1)
For Co3O4Or any one in CoO;The nickel oxide is Ni2O3Or any one in NiO.
With reference to first aspect, in second of possible embodiment of first aspect, by the green compact in step (5)
Being placed in the method that Muffle furnace high temperature is calcined is:The green compact is warming up in Muffle furnace with the heating rate of 1-10 DEG C/min
1200-1500 DEG C, and calcining at constant temperature 20-30 hours, after be slowly cooled to room temperature with stove.
With reference to first aspect, in the third possible embodiment of first aspect, what is obtained in step (6) described receives
Rice (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder be flaky nanometer structure, BET specific surface area 26.38-32.43m2g-1, hole
Diameter is between 2-13nm.
Second aspect utilizing above-mentioned nanometer (Mg the present invention provides a kind of0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparations
Lithium ion battery negative material is formed by following constituent mass percentages:(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders
70%, acetylene black 20%, binder 10%.
Compared with prior art, one or more technical solutions provided by the invention, at least have the following technical effects or advantages:
The present invention uses high temperature solid-state method one-step synthesis (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O block materials, then pass through height
Energy ball-milling method obtains the nanometer (Mg of structure in the form of sheets0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder, operating procedure is simple, it is at low cost,
It is pollution-free.
The present invention utilizes the nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O prepare lithium ion battery negative material,
Higher specific capacity can be kept under the charging and discharging currents density of 100mA/g, and there is excellent cyclical stability.Multiplying power is filled
Discharge test shows that it is still with good stability under the charging and discharging currents density successively increased, when current density increases
When adding to 1000mA/g, specific capacity is stablized in 690mAh/g;When current density increases to 2000mA/g, specific capacity is stablized
600mAh/g;And when current density is decreased to 100mA/g, specific capacity can be restored completely substantially, and specific capacity is stablized
1090mAh/g or so.
Description of the drawings
Fig. 1 is the nanometer (Mg of 1 gained of the embodiment of the present invention0.2Co0.2Ni0.2Cu0.2Zn0.2) O XRD spectrum;
Fig. 2 is 1 gained nanometer (Mg of the embodiment of the present invention0.2Co0.2Ni0.2Cu0.2Zn0.2) O Flied emission scanning electron microscopy
Mirror figure;
Fig. 3 is 1 gained nanometer (Mg of the embodiment of the present invention0.2Co0.2Ni0.2Cu0.2Zn0.2) O Flied emission transmission electron microscopy
Mirror figure;
Fig. 4 a are 1 gained nanometer (Mg of the embodiment of the present invention0.2Co0.2Ni0.2Cu0.2Zn0.2) O N2Absorption/desorption isothermal is bent
Line;
Fig. 4 b are 1 gained nanometer (Mg of the embodiment of the present invention0.2Co0.2Ni0.2Cu0.2Zn0.2) O Barrett-Joyner-
Halenda pore size distribution curves;
Fig. 5 is that the lithium ion battery negative material of 5 gained of the embodiment of the present invention measures under different charging and discharging currents density
Cycle characteristics;
Fig. 6 is cycle of the lithium ion battery negative material of 5 gained of the embodiment of the present invention under the current density of 100mA/g
Characteristic.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific terminology), there is meaning identical with the general understanding of the those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, it should be understood that have in the context of the prior art
The consistent meaning of meaning, and unless by specific definitions, otherwise will not be explained with the meaning of idealization or too formal.
Embodiment 1
A kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method:
(1) MgO (0.1mol, 4.030g), Co that purity is higher than 99.99% are weighed3O4(0.0333mol, 8.027g),
Ni2O3(0.05mol, 8.269g), CuO (0.1mol, 7.954g) and ZnO (0.1mol, 8.139g) are packed into ZrO2In ball grinder;
Ratio of grinding media to material 10 is pressed again:1-20:1 is packed into ZrO2Abrading-ball;
(2) ball grinder sealed, vacuumize, be filled with inert gas;
(3) ball grinder is installed on high energy ball mill, and covers outer cover, connected under 1000-2000r/min rotating speeds
Continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
(4) the obtained composite powder is packed into mold, then with tablet press machine by its cold moudling, be made 1cm × 1cm ×
The green compact of 0.5cm;
(5) green compact being placed in the calcining of Muffle furnace high temperature, calcination temperature is 1200 DEG C, and soaking time is 20 hours,
Then it cools to room temperature with the furnace, obtains (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
(6) (the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks continuous high-energy ball in ethyl alcohol-isopropyl alcohol mixed solvent
Mill 60 hours, obtains nanometer (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder.
Fig. 1-4 is the (Mg to gained in embodiment 10.2Co0.2Ni0.2Cu0.2Zn0.2) obtained by O nanometer powders are characterized
Picture.Wherein:
Fig. 1 is the (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders XRD spectrum, wherein abscissa be 2 diffraction
Angle, ordinate are diffracted intensity, the spectral line of the spectral line and the magnesia with face-centered cubic crystal structure in JCPDS databases
PDF-#45-0946 shows the (Mg obtained by the embodiment of the present invention as mild as a dove0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometers
Powder is single-phase (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O solid solution.
Fig. 2 and Fig. 3 is respectively (Mg described in embodiment 10.2Co0.2Ni0.2Cu0.2Zn0.2) Flied emissions of O nanometer powders sweeps
Electron microscope picture and Flied emission transmission electron microscope figure are retouched, shows (the Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nano powders
End is flaky nanometer structure.
Fig. 4 a are (Mg described in embodiment 10.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders N2Absorption/desorption isothermal is bent
Line, Fig. 4 b are its Barrett-Joyner-Halenda pore size distribution curve, and wherein Relative pressure are opposite pressure
Power, Quanity Adsorbed are adsorbance, and Pore Diameter are aperture, and Pore Volume are Kong Rong, Adsorption
For absorption, Desorption is desorption.Fig. 4 a and Fig. 4 b show the (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders
BET specific surface area is 26.38m2g-1, aperture is between 2-10nm.
Embodiment 2
A kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method:
(1) MgO (0.1mol, 4.030g) of the purity higher than 99.99%, CoO (0.1mol, 7.493g), NiO are weighed
(0.1mol, 7.469g), CuO (0.1mol, 7.954g) and ZnO (0.1mol, 8.139g) are packed into ZrO2In ball grinder;It presses again
Ratio of grinding media to material 10:1-20:1 is packed into ZrO2Abrading-ball;
(2) ball grinder sealed, vacuumize, be filled with inert gas;
(3) ball grinder is installed on high energy ball mill, and covers outer cover, connected under 1000-2000r/min rotating speeds
Continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
(4) the obtained composite powder is packed into mold, then with tablet press machine by its cold moudling, be made 1cm × 1cm ×
The green compact of 0.5cm;
(5) green compact being placed in the calcining of Muffle furnace high temperature, calcination temperature is 1300 DEG C, and soaking time is 20 hours,
Then it cools to room temperature with the furnace, obtains (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
(6) (the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks continuous high-energy ball in ethyl alcohol-isopropyl alcohol mixed solvent
Mill 60 hours, obtains (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders.
Embodiment 3
A kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method:
(1) MgO (0.1mol, 4.030g), Co that purity is higher than 99.99% are weighed3O4(0.0333mol, 8.027g), NiO
(0.1mol, 7.469g), CuO (0.1mol, 7.954g) and ZnO (0.1mol, 8.139g) are packed into ZrO2In ball grinder;It presses again
Ratio of grinding media to material 10:1-20:1 is packed into ZrO2Abrading-ball;
(2) ball grinder sealed, vacuumize, be filled with inert gas;
(3) ball grinder is installed on high energy ball mill, and covers outer cover, connected under 1000-2000r/min rotating speeds
Continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
(4) the obtained composite powder is packed into mold, then with tablet press machine by its cold moudling, be made 1cm × 1cm ×
The green compact of 0.5cm;
(5) green compact being placed in the calcining of Muffle furnace high temperature, calcination temperature is 1200 DEG C, and soaking time is 25 hours,
Then it cools to room temperature with the furnace, obtains (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
(6) (the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks continuous high-energy ball in ethyl alcohol-isopropyl alcohol mixed solvent
Mill 60 hours, obtains (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders.
Embodiment 4
A kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method:
(1) MgO (0.1mol, 4.030g) of the purity higher than 99.99%, CoO (0.1mol, 7.493g), Ni are weighed2O3
(0.05mol, 8.269g), CuO (0.1mol, 7.954g) and ZnO (0.1mol, 8.139g) are packed into ZrO2In ball grinder;It presses again
Ratio of grinding media to material 10:1-20:1 is packed into ZrO2Abrading-ball;
(2) ball grinder sealed, vacuumize, be filled with inert gas;
(3) ball grinder is installed on high energy ball mill, and covers outer cover, connected under 1000-2000r/min rotating speeds
Continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
(4) the obtained composite powder is packed into mold, then with tablet press machine by its cold moudling, be made 1cm × 1cm ×
The green compact of 0.5cm;
(5) green compact being placed in the calcining of Muffle furnace high temperature, calcination temperature is 1300 DEG C, and soaking time is 20 hours,
Then it cools to room temperature with the furnace, obtains (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
(6) (the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks continuous high-energy ball in ethyl alcohol-isopropyl alcohol mixed solvent
Mill 65 hours, obtains (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders.
Embodiment 2-4 products therefroms are characterized, are obtained and the extremely similar test result of embodiment 1.As implemented
The peak position and peak shape of the XRD spectrum diffraction maximum of 2,3,4 products therefrom of example are identical as Fig. 1, this illustrates that embodiment 2-4 is prepared into
(the Mg with face-centered cubic crystal structure is arrived0.2Co0.2Ni0.2Cu0.2Zn0.2) O solid solution;N2Absorption/desorption test result table
Its bright BET specific surface area is 26.38-32.43m2g-1, aperture is between 2-13nm.
Embodiment 5
It is a kind of to utilize above-mentioned (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders prepare negative electrode of lithium ion battery material
Material is formed by following constituent mass percentages:(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders 70%, acetylene black 20%,
Binder 10%.
It in charging and discharging currents density is 100mA/g, 200mA/ that Fig. 5, which is lithium ion battery negative material described in embodiment 5,
G, the cycle measured under 500mA/g, 1000mA/g, 2000mA/g, 3000mA/g, 1000mA/g, 200mA/g and 100mA/g is special
Property, wherein Cycle Number are cycle-index, and Specific Capacity are specific capacity, and Discharge Capacity are
Discharge capacity, Charge Capacity are charging capacity.
Fig. 6 is cycle characteristics of the lithium ion battery negative material under the current density of 100mA/g described in embodiment 5,
Wherein Cycle Number are cycle-index, and Specific Capacity are specific capacity, and Discharge Capacity are electric discharge
Capacity, Charge Capacity are charging capacity.
It still has good stabilization under the charging and discharging currents density successively increased as can be known from Fig. 5 and Fig. 6
Property, when current density increases to 1000mA/g, specific capacity is stablized in 690mAh/g;When current density increases to 2000mA/g
When, specific capacity is stablized in 600mAh/g;And when current density is decreased to 100mA/g, specific capacity can be restored completely substantially, and compare
Capacity is stablized in 1090mAh/g or so.
The present invention is not limited to above-mentioned optional embodiment, anyone can show that other are various under the inspiration of the present invention
The product of form, however, make any variation in its shape or structure, it is every to fall into the claims in the present invention confining spectrum
Technical solution, be within the scope of the present invention.
Claims (5)
1. a kind of nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method, which is characterized in that include the following steps:
Step (1):First magnesia of the purity higher than 99.99%, cobalt oxide, oxygen are weighed by equimolar metallic atom stoichiometric ratio
Change nickel, copper oxide and Zinc oxide powder, and is packed into ZrO2In ball grinder;Ratio of grinding media to material 10 is pressed again:1-20:1 is packed into ZrO2Abrading-ball;
Step (2):The ball grinder is sealed, and is vacuumized, inert gas is then charged with;
Step (3):The ball grinder is installed on high energy ball mill, and covers outer cover, under 1000-2000r/min rotating speeds
Continuous ball milling 3-6 hours, obtains the composite powder of grain size 10-100nm;
Step (4):The obtained composite powder is packed into mold, then 1cm × 1cm is made in its cold moudling with tablet press machine
The green compact of × 0.5cm;
Step (5):By the green compact be placed in Muffle furnace high temperature calcining, after be slowly cooled to room temperature, obtain
(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks;
Step (6):(the Mg by described in0.2Co0.2Ni0.2Cu0.2Zn0.2) O blocks continuous high-energy in ethyl alcohol-isopropyl alcohol mixed solvent
Ball milling 60-70 hours obtains nanometer (Mg of the grain size between 10-100nm0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder.
2. nanometer (Mg according to claim 10.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method, which is characterized in that step
Suddenly the cobalt oxide in (1) is Co3O4Or any one in CoO;The nickel oxide is Ni2O3Or it is any one in NiO
Kind.
3. nanometer (Mg according to claim 10.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method, which is characterized in that
It is by the method that the green compact is placed in the calcining of Muffle furnace high temperature in step (5):The green compact in Muffle furnace with 1-10 DEG C/
The heating rate of min is warming up to 1200-1500 DEG C, and calcining at constant temperature 20-30 hours, after be slowly cooled to room temperature with stove.
4. nanometer (Mg according to claim 10.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method, which is characterized in that step
Suddenly nanometer (the Mg obtained in (6)0.2Co0.2Ni0.2Cu0.2Zn0.2) O powder be flaky nanometer structure, BET specific surface area
For 26.38-32.43m2g-1, aperture is between 2-13nm.
5. a kind of utilizing nanometer (Mg described in claim 10.2Co0.2Ni0.2Cu0.2Zn0.2) O prepare negative electrode of lithium ion battery
Material, which is characterized in that the lithium ion battery negative material is formed by following constituent mass percentages:
(Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O nanometer powders 70%, acetylene black 20%, binder 10%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810587675.9A CN108682840B (en) | 2018-06-08 | 2018-06-08 | Nanometer (Mg)0.2Co0.2Ni0.2Cu0.2Zn0.2) Preparation method and application of O |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810587675.9A CN108682840B (en) | 2018-06-08 | 2018-06-08 | Nanometer (Mg)0.2Co0.2Ni0.2Cu0.2Zn0.2) Preparation method and application of O |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108682840A true CN108682840A (en) | 2018-10-19 |
CN108682840B CN108682840B (en) | 2021-06-15 |
Family
ID=63810425
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810587675.9A Expired - Fee Related CN108682840B (en) | 2018-06-08 | 2018-06-08 | Nanometer (Mg)0.2Co0.2Ni0.2Cu0.2Zn0.2) Preparation method and application of O |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108682840B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110190259A (en) * | 2019-06-12 | 2019-08-30 | 四川大学 | A kind of preparation method and lithium ion battery negative material of the high entropy oxide of nanometer |
CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
CN110600724A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition-non-transition high-entropy oxide negative electrode material for lithium ion battery |
CN110950654A (en) * | 2019-12-16 | 2020-04-03 | 东南大学 | High-entropy magnesium aluminate spinel type complex oxide and preparation method thereof |
CN112467119A (en) * | 2020-12-02 | 2021-03-09 | 东北大学秦皇岛分校 | Preparation method and application of layered high-entropy oxide sodium-ion battery positive electrode material |
CN112614986A (en) * | 2020-12-18 | 2021-04-06 | 安徽工业大学 | Rock salt type high-entropy anode material containing sulfur-oxygen dianions and preparation method |
CN113353996A (en) * | 2021-08-09 | 2021-09-07 | 浙江大学杭州国际科创中心 | High-entropy conversion type sodium ion battery electrode material |
CN113437260A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | Single crystal battery anode material and preparation method thereof |
CN113636607A (en) * | 2021-08-03 | 2021-11-12 | 中国矿业大学 | Preparation method of high-entropy oxide of lithium ion battery negative electrode material |
CN114302862A (en) * | 2019-08-29 | 2022-04-08 | 诺沃尼克斯电池技术解决方案公司 | Lithium transition metal oxide and precursor microparticles and methods |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107994228A (en) * | 2017-12-25 | 2018-05-04 | 中国工程物理研究院电子工程研究所 | A kind of five yuan high entropy oxide nano-film of lithium ion battery and its preparation and application |
-
2018
- 2018-06-08 CN CN201810587675.9A patent/CN108682840B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107994228A (en) * | 2017-12-25 | 2018-05-04 | 中国工程物理研究院电子工程研究所 | A kind of five yuan high entropy oxide nano-film of lithium ion battery and its preparation and application |
Non-Patent Citations (1)
Title |
---|
CHRISTINA M. ROST等: "Entropy-stabilized oxides", 《NATURE COMMUNICATIONS》 * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110190259A (en) * | 2019-06-12 | 2019-08-30 | 四川大学 | A kind of preparation method and lithium ion battery negative material of the high entropy oxide of nanometer |
CN110364717A (en) * | 2019-07-24 | 2019-10-22 | 东北大学秦皇岛分校 | A kind of high entropy oxide electrode material of spinel-type and preparation method thereof |
CN114302862A (en) * | 2019-08-29 | 2022-04-08 | 诺沃尼克斯电池技术解决方案公司 | Lithium transition metal oxide and precursor microparticles and methods |
CN110556536A (en) * | 2019-09-19 | 2019-12-10 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
CN110600724A (en) * | 2019-09-19 | 2019-12-20 | 安徽工业大学 | Five-element transition-non-transition high-entropy oxide negative electrode material for lithium ion battery |
CN110600724B (en) * | 2019-09-19 | 2022-08-02 | 安徽工业大学 | Five-element transition-non-transition high-entropy oxide negative electrode material for lithium ion battery |
CN110556536B (en) * | 2019-09-19 | 2022-06-14 | 安徽工业大学 | Six-element high-entropy oxide material for lithium ion battery and preparation method thereof |
CN110950654A (en) * | 2019-12-16 | 2020-04-03 | 东南大学 | High-entropy magnesium aluminate spinel type complex oxide and preparation method thereof |
CN112467119A (en) * | 2020-12-02 | 2021-03-09 | 东北大学秦皇岛分校 | Preparation method and application of layered high-entropy oxide sodium-ion battery positive electrode material |
CN112614986A (en) * | 2020-12-18 | 2021-04-06 | 安徽工业大学 | Rock salt type high-entropy anode material containing sulfur-oxygen dianions and preparation method |
CN112614986B (en) * | 2020-12-18 | 2021-12-07 | 安徽工业大学 | Rock salt type high-entropy anode material containing sulfur-oxygen dianions and preparation method |
CN113437260A (en) * | 2021-06-29 | 2021-09-24 | 中钢天源股份有限公司 | Single crystal battery anode material and preparation method thereof |
CN113636607A (en) * | 2021-08-03 | 2021-11-12 | 中国矿业大学 | Preparation method of high-entropy oxide of lithium ion battery negative electrode material |
CN113353996B (en) * | 2021-08-09 | 2021-11-05 | 浙江大学杭州国际科创中心 | High-entropy conversion type sodium ion battery electrode material |
CN113353996A (en) * | 2021-08-09 | 2021-09-07 | 浙江大学杭州国际科创中心 | High-entropy conversion type sodium ion battery electrode material |
Also Published As
Publication number | Publication date |
---|---|
CN108682840B (en) | 2021-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108682840A (en) | Nanometer (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2) O preparation method and application | |
CN110190259B (en) | Preparation method of nano high-entropy oxide and lithium ion battery negative electrode material | |
Jiang et al. | Preparation and rate capability of Li4Ti5O12 hollow-sphere anode material | |
CN101164870B (en) | Method for manufacturing high performance composite phase lithium iron phosphate material | |
JP2019021626A (en) | Spherical or spheroidal lithium ion battery positive electrode material and lithium ion battery | |
KR102433699B1 (en) | Ion conductors and power storage devices | |
EP2544270A1 (en) | Positive electrode active material for lithium-ion battery, positive electrode for lithium-ion battery, and lithium-ion battery | |
CN101752555A (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
CN101777644A (en) | Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate | |
JP2008226741A (en) | Composite powder for electrode and its manufacturing method | |
Zhang et al. | Phase transformation and cycling characteristics of a Ce 2 Ni 7-type single-phase La 0.78 Mg 0.22 Ni 3.45 metal hydride alloy | |
WO2023124574A1 (en) | Titanium and zirconium co-doped, carbon-coated lithium iron phosphate material, preparation method therefor and use thereof | |
CN101659442B (en) | Spinel structure lithium titanate and preparation method and application thereof | |
CN113871702A (en) | Preparation of Geranite type solid electrolyte and all-solid-state battery application thereof | |
CN102709548A (en) | Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material | |
Shun et al. | Zn 0.5 Co 0.5 Mn 0.5 Fe 0.5 Al 0.5 Mg 0.5 O 4 high-entropy oxide with high capacity and ultra-long life for Li-ion battery anodes. | |
Zhang et al. | A new AB4-type single-phase superlattice compound for electrochemical hydrogen storage | |
CN103199236B (en) | Adulterated lithium manganate presoma, modified lithium manganate cathode material and preparation method thereof | |
JP7050465B2 (en) | Manufacturing method of solid electrolyte for all-solid-state secondary battery, all-solid-state secondary battery, and solid electrolyte | |
WO2024093126A1 (en) | Layered sodium-ion battery positive electrode material, preparation method therefor, and use thereof | |
CN1754972A (en) | High-capacity rare earth-magnesium based multi-phase hydrogen strage alloy for MH-Ni battery and its preparation method | |
CN104518210B (en) | A kind of preparation method of composite titanic acid lithium material | |
WO2021251405A1 (en) | Solid electrolyte material, solid electrolyte, production methods therefor, and all-solid-state battery | |
CN102569795A (en) | Comprehensive modification method for synthesis of lithium iron phosphate | |
WO2014022989A1 (en) | Doped secondary battery positive electrode material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210615 |