CN104671293A - Hierarchically layered monometal hydroxide as well as synthesis method and application thereof - Google Patents
Hierarchically layered monometal hydroxide as well as synthesis method and application thereof Download PDFInfo
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- CN104671293A CN104671293A CN201510053092.4A CN201510053092A CN104671293A CN 104671293 A CN104671293 A CN 104671293A CN 201510053092 A CN201510053092 A CN 201510053092A CN 104671293 A CN104671293 A CN 104671293A
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- monometallic
- oxyhydroxide
- stratiform
- hierarchical organization
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Abstract
The invention discloses a synthesis method of a hierarchically layered monometal hydroxide. The synthesis method comprises the following steps: firstly, mixing sodium cyanate with water to obtain a solution A, and mixing a soluble salt of a metal M with water to obtain a solution B, wherein the mass concentration of the solution A is 0.03-0.5mol/L, the mass concentration of the solution B is 0.01-1mol/L, and the metal M is Ni or Co; then adding the solution B into the solution A which has the same volume as the solution B, stirring, and carrying out reaction to obtain a precipitate; and finally posttreating the precipitate to obtain the hierarchically layered monometal hydroxide. The hierarchically layered monometal hydroxide is prepared on a large scale in a suitable alkaline condition which is created by hydrolyzing nontoxic low-cost sodium cyanate at room temperature. The synthesis method disclosed by the invention is universal, simple and controllable, omits the procedure of heating, adopts no additional structure-directing agents, is high in cost-performance ratio and can be applied widely, and the hierarchically layered monometal hydroxide synthesized by adopting the synthesis method has excellent electrochemical properties.
Description
Technical field
The present invention relates to the preparation field of nano material, particularly relate to a kind of there is hierarchical organization stratiform monometallic oxyhydroxide and synthetic method and application.
Background technology
Ultracapacitor is a kind of environmental friendliness between traditional capacitor and rechargeable battery, the novel energy-storing that can not be substituted, energy saver.It had both had electrical condenser can the feature of fast charging and discharging, has again the energy storage mechnism of electrochemical cell.Compared with traditional capacitor, ultracapacitor has high power density, long circulation life, the features such as pollution-free, wider operating temperature range, and the application therefore in the fields such as electromobile, communication, electronic signal monitoring is more and more concerned.
Two-dimensional layer double-hydroxide (LDH) is a class ion lamellar compound, is made up of the layer body with houghite (brucite) structure of positively charged and the negatively charged ion of interlayer band compensation negative charge.The general formula of LDH can use [M
2+ 1-xm
3+ x(OH)
2[A
n-] zH
2o represents, wherein M
2+, M
3+represent the positively charged ion of divalence and trivalent respectively, A
n-for the charge-balancing species of non-composition framework.Wherein studies have reported that some comprise α-Ni (OH)
2with α-Co (OH)
2interior be only the promising ultracapacitor active material of tool containing the LDHs of divalent metal.Although LDHs general electrons/ions electroconductibility is not high, when having good nanostructure, LDHs class material can show excellent electrochemical activity.In recent years, nano science research finds that nano particle carries out meeting after grade assembling, and the coupling between nano unit can make whole bill of material reveal new physical properties.For LDHs class material, it belongs to stratified material from crystallographic structure, therefore the elementary forming core unit of LDHs often forms nanometer sheet in building-up process, and utilize nanometer sheet unit to carry out ordered structure that grade is assembled into high-order may improve material greatly as the stored energy capacitance of ultracapacitor active substance and cyclical stability.But the LDHs material that cheap extensive preparation has ordered fabrication structure is still very challenging.
Cheap synthesis comprises α-Ni (OH)
2with α-Co (OH)
2following difficulty is faced with at interior stratiform monometallic oxyhydroxide.First, the α phase oxyhydroxide of Ni and Co can change β phase under basic conditions.In order to provide moderate alkalescence, the method that tradition uses adds a large amount of reagent as the slow hydrolysis release alkaline matter in a heated condition such as urea or urotropin (HMT).Under this condition, heating is for a long time needed to provide Energy Decomposition these precipitation agents, uneconomical from energy point of view.The second, have in the material synthesis processes of ordered nano-structure and often need to use the structure directing agent as tensio-active agent or template and so on, extra cost can be brought like this.3rd, when synthesis scale being amplified, only use large container that nonlinear experiment condition can be brought to change, comprise reagent addition manner, the distribution of heating condition and chemical environment and temperature, these changes can reduce product quality.Therefore, exploitation is a kind of general, can amplify scale, and without the need to heating, without the need to tensio-active agent, simply, controlled and cheap method is synthesized the LDHs with excellent fake capacitance performance and will be of practical significance very much.
Summary of the invention
The present invention utilizes nontoxic, and the By Hydrolysis At Room Temperature of cheap cyanic acid sodium salt provides suitable alkaline condition, has prepared the stratiform monometallic oxyhydroxide with hierarchical organization on a large scale.The method has versatility, and without the need to heating, without the need to supernumerary structure directed agents, simply, controlled, cost performance is high, resulting materials electrochemical performance, and this technology has a wide range of applications meaning.
There is a synthetic method for the stratiform monometallic oxyhydroxide of hierarchical organization, comprise the following steps:
(1) Zassol and water are mixed to get solution A, and soluble salt and the water of metal M are mixed to get solution B;
The mass concentration of described solution A is 0.03 ~ 0.5mol/L;
Described metal M is Ni or Co;
(2) join in solution A by solution B, stirring reaction is precipitated, then obtains the described stratiform monometallic oxyhydroxide with hierarchical organization through aftertreatment.
Principle of the present invention:
In the present invention, Zassol (NaNCO) is a kind of nontoxic, and the salt be cheaply easy to get, cyanic acid HNCO is a kind of weak acid, its conjugate anion NCO
-performance alkalescence can be hydrolyzed.And comprise Ni
2+and Co
2+can be hydrolyzed aobvious acid in water at interior transition metal ion.Therefore, when two kinds of ions coexist in water, they can mutual facilitation of hydrolysis process thus commonly known pair of hydrolysis reaction occurs.Ni simultaneously
2+and Co
2+be easy to and nitrogen-atoms with lone-pair electron to body (N-) and π key ligand complex, NCO
-structure in there is these features.Complex reaction will change the concentration of free metal ion in solution and then provide controllability for whole reaction.In the synthetic method of this patent report, only need the aqueous solution of NaNCO and the transition metal ion aqueous solution (N directly
i2+, Co
2+) mixing, by controlling hybrid mode and speed, get final product the divalence monometallic layered metal hydroxides that controlled synthesis has different grades structure, although these three-dimensional structures are all made up of basic nanometer sheet, but different couplings makes final chemical property have larger difference.Comprise α-Ni (OH)
2with α-Co (OH)
2be assembled in high-order three-dimensional structure process further in its nanometer sheet of interior material, the chemical environment on surface and edge that its assembly behavior is subject to nanometer sheet controls, and is also namely subject to containing NCO
-the aqueous solution in NCO
-concentration control.Therefore contain the aqueous solution of NaNCO by control and contain the transition metal ion aqueous solution (N
i2+, Co
2+) mixing velocity can control products therefrom structure.At present, not yet there are document or patent report that NaNCO is applied to Inorganic synthese field.
In step (1), described solution A is the aqueous solution of NaNCO, and during different concns, its pH value range is stabilized in 9.5 ~ 10.5, but the concentration of the NaNCO aqueous solution greatly can affect the structure of reaction product.When strength of solution is too high, larger region degree of supersaturation will affect product uniformity.As preferably, the mass concentration of described solution A is 0.05 ~ 0.1mol/L, and under this concentration, product amount is comparatively large, and when concentration can be avoided again excessive, more complicated hydrolytic process affects product quality.
The concentration of solution B also has certain influence to product structure, but relatively the concentration impact of NaNCO is less, and as preferably, in step (1), the mass concentration of described solution B is 0.015 ~ 0.2mol/L; More preferably 0.015 ~ 0.05mol/L.Higher output and good product quality can be obtained under preferred concentration.
As preferably, in step (1), the soluble salt of described metal M is the muriate of metal M.
Find after deliberation, the blending means of two kinds of solution has a great impact product structure, and in general, when solution B is added solution A, the nanometer sheet unit of products therefrom is little, is easily assembled into three-dimensional structure; If when A is added B, nanometer sheet unit is large, and the easy composite structure of lengthy motion picture in further growth nanometer sheet formation sheet in large nanometer sheet substrate.
As preferably, in step (2), solution B joins in isopyknic solution A, to ensure optimal hydrolysis environment.
The speed that adds of solution B also has impact to region degree of supersaturation, and as preferably, the speed that adds of solution B is 2 ~ 20mL/min, and now reaction time consumption is shorter, and solution region degree of supersaturation is controlled, and product structure is even.
As preferably, in step (2), described stirring velocity is 500 ~ 1000rpm, and churning time is 1.5 ~ 24h.After solution B adds completely, churning time is little on product impact, churning time can be controlled at 3h for raising the efficiency.
As preferably, in step (2), described aftertreatment comprises cooling, washing, dry.
As preferably, described drying temperature is 60 ~ 100 DEG C.Drying temperature is little on product impact, if but temperature is too low, and drying efficiency is lower, and temperature is too high, can increase energy consumption, can select drying temperature according to actual needs.
According to above-mentioned preferred reason:
When described stratiform monometallic oxyhydroxide is α-Ni (OH)
2time,
The mass concentration of described solution A is 0.04 ~ 0.06mol/L, and the mass concentration of solution B is 0.01 ~ 0.02mol/L, and the speed that adds of solution B is 2 ~ 5mL/min;
Further preferably, the mass concentration of described solution A is 0.05mol/L, and the mass concentration of solution B is 0.015mol/L, and the speed that adds of solution B is 4mL/min.
When described stratiform monometallic oxyhydroxide is α-Co (OH)
2time,
The mass concentration of described solution A is 0.08 ~ 0.12mol/L, and the mass concentration of solution B is 0.04 ~ 0.06mol/L, and the speed that adds of solution B is 8 ~ 12mL/min;
Further preferably, the mass concentration of described solution A is 0.1mol/L, and the mass concentration of solution B is 0.05mol/L, and the speed that adds of solution B is 10mL/min.
The invention also discloses the stratiform monometallic oxyhydroxide with hierarchical organization according to the synthesis of described method.Be assembled into high-order three-dimensional connecting structure (3D-ICHA) further by basic nanometer sheet, demonstrate interaction force strong between nanometer sheet by this material skeleton stretch breaking process of transmission electron microscope (TEM) electron beam-induced phase change technique home position observation.Meanwhile, this material specific surface area is up to 300 ~ 350m
2g
-1, its pore size distribution concentrates on 4.0 ~ 30.0nm.When desirable surface and strong packaging assembly make this material as ultracapacitor active substance, show high capacity and good cyclical stability.
The present invention further discloses again the described application of stratiform monometallic oxyhydroxide in ultracapacitor with hierarchical organization, with α-Ni (OH)
2for example, known through performance test, the α-Ni (OH) of 3D-ICHA
2the top performance of initial capacity and existing bibliographical information is suitable, and significantly more than the Ni (OH) of the α thing phase had been reported
2.
Compared with prior art, the present invention has following outstanding advantages:
Preparation method of the present invention utilizes nontoxic, and the By Hydrolysis At Room Temperature of cheap cyanic acid sodium salt provides suitable alkaline condition, has prepared the stratiform monometallic oxyhydroxide with hierarchical organization on a large scale.The method has versatility, and without the need to heating, without the need to supernumerary structure directed agents, simply, controlled, cost performance is high, resulting materials electrochemical performance, and this technology has a wide range of applications meaning;
Reaction conditions of the present invention is gentle, and without the need to carrying out under high temperature, high pressure and inert atmosphere, therefore low to the requirement of equipment, fund input is few, and this reaction time consumption is short, decreases energy consumption, is applicable to large-scale industrial production;
α-the Ni (OH) of what the present invention prepared have three-dimensional bridging arrangement
2stability Analysis of Structures, has up to 320.2m
2g
-1specific surface area.As ultracapacitor active material, at 1A g
-1current density under, initial ratio capacitance is up to 2139.3F g
-1, at 10A g
-1under high current density, circulation still has the capability retention of 86.2% for 20000 times, and this performance is at the α-Ni (OH) higher than current bibliographical information
2powder electrode is as the performance of ultracapacitor active substance.
Accompanying drawing explanation
Fig. 1 is 3D-ICHA α-Ni (OH) prepared by embodiment 1
2xRD figure;
Fig. 2 is 3D-ICHA α-Ni (OH) prepared by embodiment 1
2sEM figure under different amplification;
Fig. 3 is the 3D-ICHA α-Ni (OH) prepared with embodiment 1
2as the cycle performance figure of the ultracapacitor of active material assembling.
Embodiment
Embodiment 1
NaNCO is directly put into water, stirs after dissolving, obtain the solution A that volumetric molar concentration is 0.05mol/L; By NiCl
26H
2o directly puts into water, stirs after dissolving, obtains the solution B that volumetric molar concentration is 0.015mol/L; By the solution A of 1L and the solution B of 1L, solution A is stirred with the speed of 500rpm, solution B is added gradually solution A mixing by peristaltic pump in whipping process with 4mL/min speed, after B adds completely, continue to stir 3h.Afterwards by the throw out that obtains after washing, drying, obtain described can be used for ultracapacitor α-Ni (OH)
2.
Fig. 1 is the XRD figure spectrum of gained sample, with α-Ni (OH)
2standard diagram fit like a glove, illustrate that product is α-Ni (OH)
2.Fig. 2 is the SEM picture of product, can find out that product is the flower-shaped aggregate structure of 100-200nm size.From Fig. 1 ~ 2, the α-Ni (OH) of this enforcement preparation
2have the structure of three-dimensional overlap joint, its specific surface area is 320.2m
2g
-1.
Comparative example
NaNCO is directly put into water, stirs after dissolving, obtain the solution A that volumetric molar concentration is 0.05mol/L; By NiCl
26H
2o directly puts into water, stirs after dissolving, obtains the solution B that volumetric molar concentration is 0.015mol/L; By the solution A of 1L and the solution B of 1L, solution A is stirred with the speed of 500rpm, solution A is added gradually solution B mixing by peristaltic pump in whipping process with 4mL/min speed, after A adds completely, continue to stir 3h.Afterwards by the throw out that obtains after washing, drying, obtain described can be used for ultracapacitor α-Ni (OH)
2.
α-the Ni (OH) of this enforcement preparation
2pattern be different from embodiment 1, by α-Ni (OH)
2nanometer sheet is self-assembled into wire or tabular, microscopic appearance disunity, and its specific surface area is 65.2m
2g
-1.
Embodiment 2
NaNCO is directly put into water, stirs after dissolving, obtain the solution A that volumetric molar concentration is 0.1mol/L; By CoCl
26H
2o directly puts into water, stirs after dissolving, obtains the solution B that volumetric molar concentration is 0.05mol/L; By the solution A of 1L and the solution B of 1L, solution A is stirred with the speed of 500rpm, solution B is added gradually solution A mixing by peristaltic pump in whipping process with 10mL/min speed, after B adds completely, continue to stir 3h.Afterwards by the throw out that obtains after washing, drying, obtain described can be used for ultracapacitor α-Co (OH)
2.
α-Co (OH) prepared by the present embodiment
2still there is the structure of three-dimensional overlap joint, but its specific surface area is slightly low, is 280.2m
2g
-1.
Embodiment 3
NaNCO is directly put into water, stirs after dissolving, obtain the solution A that volumetric molar concentration is 0.5mol/L; By NiCl
26H
2o directly puts into water, stirs after dissolving, obtains the solution B that volumetric molar concentration is 0.15mol/L; By the solution A of 1L and the solution B of 1L, solution A is stirred with the speed of 500rpm, solution B is added gradually solution A mixing by peristaltic pump in whipping process with 4mL/min speed, after B adds completely, continue to stir 3h.Afterwards by the throw out that obtains after washing, drying, obtain described can be used for ultracapacitor α-Ni (OH)
2.
α-the Ni (OH) of this enforcement preparation
2have loose stacking provisions, its specific surface area is 72.0m
2g
-1.
Performance test
With 3D-ICHA α-Ni (OH) prepared by embodiment 1
2nanometer sheet prepares ultracapacitor as electrode materials, and preparation method is as follows:
3D-ICHA α-the Ni (OH) that embodiment 1 is prepared
2nanometer sheet mixes in the ratio of 80:10:10 with tackiness agent poly(vinylidene fluoride) (PVDF) and conductive agent acetylene black as electrode active material, add 1-Methyl-2-Pyrrolidone (NMP) again and be stirred into slurry, evenly be coated in nickel foam surface, then at 85 DEG C, dry 12h and obtain electrode slice.Electrode slice is placed in vacuum drying oven again in 90 DEG C of dry 8h after roll squeezer compacting, divides and cut into supercapacitor positive electrode sheet.
The electrode slice made is assembled into three-electrode system and carries out Performance Detection, Pt metal sheet is as 3D-ICHA α-Ni (OH)
2to electrode, electrolytic solution is the aqueous solution containing 1mol/L KOH, and reference electrode is be immersed in the Hg/HgO electrode in the 1M KOH aqueous solution.The ultracapacitor assembled carries out constant current charge-discharge test after circulation activation in 10 weeks, charging/discharging voltage is 0.01 ~ 0.55V, at 25 ± 2 DEG C of environment with 10A/g constant current charge-discharge loop test (rate of charge is identical with corresponding discharge-rate), test reversible capacity and the charge-discharge performance of this ultracapacitor.
Cycle performance test result as shown in Figure 3, the 3D-ICHA α-Ni (OH) obtained with the present invention
2the ultracapacitor prepared for positive electrode material has higher reversible capacity and cycle performance, at 10A g
-1under current density after 20000 charge and discharge cycles specific storage still higher than 1200F/g.
Claims (10)
1. there is a synthetic method for the stratiform monometallic oxyhydroxide of hierarchical organization, it is characterized in that, comprise the following steps:
(1) Zassol and water are mixed to get solution A, and soluble salt and the water of metal M are mixed to get solution B;
The mass concentration of described solution A is 0.03 ~ 0.5mol/L, and the mass concentration of solution B is 0.01 ~ 1mol/L;
Described metal M is Ni or Co;
(2) join in solution A by solution B, stirring reaction is precipitated, then obtains the described stratiform monometallic oxyhydroxide with hierarchical organization through aftertreatment.
2. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1, is characterized in that, in step (1), the mass concentration of described solution A is 0.05 ~ 0.1mol/L.
3. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1, is characterized in that, in step (1), the mass concentration of described solution B is 0.015 ~ 0.2mol/L.
4. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1, is characterized in that, in step (1), the soluble salt of described metal M is the muriate of metal M.
5. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1 or 3, it is characterized in that, in step (2), solution B joins in isopyknic solution A, and adding speed is 2 ~ 20mL/min.
6. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1, is characterized in that, in step (2), described stirring velocity is 500 ~ 1000rpm, and churning time is 1.5 ~ 24h.
7. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 1, is characterized in that, in step (2), described aftertreatment comprises cooling, washing, drying.
8. the synthetic method with the stratiform monometallic oxyhydroxide of hierarchical organization according to claim 7, it is characterized in that, described drying temperature is 60 ~ 100 DEG C.
9. the stratiform monometallic oxyhydroxide with hierarchical organization of a method synthesis according to claim 1.
10. the application of stratiform monometallic oxyhydroxide in ultracapacitor with hierarchical organization according to claim 9.
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Citations (3)
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|---|---|---|---|---|
| CN102807255A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院大连化学物理研究所 | Flower-like nanometer cobalt hydroxide material and preparation method thereof |
| CN102826617A (en) * | 2012-09-21 | 2012-12-19 | 中国科学院过程工程研究所 | Spherical nickel hydroxide material and preparation method thereof |
| CN104016423A (en) * | 2014-06-06 | 2014-09-03 | 安徽师范大学 | Preparation method of magnetic metal alpha phase hydroxide nanometer material as well as super-capacitor electrode |
-
2015
- 2015-02-02 CN CN201510053092.4A patent/CN104671293B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807255A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院大连化学物理研究所 | Flower-like nanometer cobalt hydroxide material and preparation method thereof |
| CN102826617A (en) * | 2012-09-21 | 2012-12-19 | 中国科学院过程工程研究所 | Spherical nickel hydroxide material and preparation method thereof |
| CN104016423A (en) * | 2014-06-06 | 2014-09-03 | 安徽师范大学 | Preparation method of magnetic metal alpha phase hydroxide nanometer material as well as super-capacitor electrode |
Non-Patent Citations (1)
| Title |
|---|
| JEONG WOO LEE ET AL.: "Hierarchical Microspheres Based on α-Ni(OH)2 Nanosheets Intercalated with Different Anions: Synthesis, Anion Exchange, and Effect of Intercalated Anions on Electrochemical Capacitance", 《J. PHYS. CHEM. C》 * |
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