CN104112848B - A kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material and preparation method thereof - Google Patents
A kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material and preparation method thereof Download PDFInfo
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- CN104112848B CN104112848B CN201410334727.3A CN201410334727A CN104112848B CN 104112848 B CN104112848 B CN 104112848B CN 201410334727 A CN201410334727 A CN 201410334727A CN 104112848 B CN104112848 B CN 104112848B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention discloses a kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, described positive electrode is prepared from by following methods: 1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water; Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve; 2) by step 1) each solution mixing of gained, at 70～80 DEG C, it is stirred vigorously 4～8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80～100 DEG C; 3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 3～5h at 300～500 DEG C, finally it is calcined 20～26h at 700 DEG C, obtains black powder and be Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material; Wherein, y=0.1～0.5. The positive electrode that the present invention prepares has good discharge capacity and capability retention.
Description
Technical field
The present invention relates to the preparation field of secondary cell, in particular it relates to a kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material and preparation method thereof.
Background technology
In recent years, along with the development of consumer electronics, electric tool and electric motor car, the demand of battery is constantly increased by market. In current existing battery system, zinc-manganse dioxide dry cell mercury pollution is prominent, capacity is not high, be not suitable for long-time heavy-current discharge, and the price of zinc is higher. Containing harmful elements Pb and Cd in plumbic acid and nickel-cadmium cell, environment is had potential danger. Achieve great progress with the battery exploitation that lithium ion battery is main representative, and be widely applied to every field. But owing to Li is active especially, it is easy at negative pole precipitating metal Li when lithium ion battery is for high current charge-discharge, thus causing potential safety hazard. This is just in the urgent need to the exploitation of cheap, safe and environment-friendly and heavy-duty battery and application. In this context, Mg secondary cell one of optionally, receives the attention of scientific research personnel. Present magnesium cell is still in the preliminary study stage, there is many an open questions. Wherein the synthesis of novel anode material and Electrochemical Properties in magnesium cell system thereof are wherein one of important research directions.
Relative to Li+, Mg2+Charge density big, solvation is even more serious, and therefore great majority may be used for the positive electrodes of lithium secondary battery and are all not directly applicable Mg secondary cell. Be generally adopted lithium as secondary cell positive electrode have following several: transient metal sulfide and organic sulfur compound, transition metal oxide, Organic substance or there is the phosphate Mg of NASICION structure0.5Ti2(PO4)3(MTP), but above-mentioned positive electrode all has certain disadvantages, and such as transient metal sulfide as positive electrode major defect is: prepare relatively difficult, it is desirable to high?temperature nuclei under vacuum or argon gas atmosphere;Easily being corroded compared with oxide, its oxidation stability is undesirable. While it is true, its good charge-discharge performance has become desirable insertion/deintercalation material. Oxide is as the positive electrode Shortcomings of Mg secondary cell: Mg2+The kinetic rate embedded is very slow; For most material, Mg in discharge process2+Embedding degree low; Most insert material cycle performances are bad, can quickly decompose in the circulating cycle. Organic substance and traditional MnO without machine battery2、HgO、CuO、Ag2O etc. compare the capacity having had, and have good cryogenic property, but along with the rising of temperature, battery capacity and cell voltage all can decline. For having the phosphate Mg of NASICION structure0.5Ti2(PO4)3(MTP), Mg2+Can at Mg0.5Ti2(PO4)3In reversible embedding/deintercalation, but they reversibilitys are subject to Mg2+The kinetics restriction of diffusion.
Summary of the invention
It is an object of the invention to, it is provided that a kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material and preparation method thereof, this positive electrode has good discharge capacity and capability retention.
For reaching above-mentioned purpose, present invention employs following technical scheme:
A kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, described positive electrode is prepared from by following methods:
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 70～80 DEG C, it is stirred vigorously 4～8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80～100 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 3～5h at 300～500 DEG C, finally it is calcined 20～26h at 700 DEG C, obtains black powder and be Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material;
Wherein, y=0.1～0.5.
Preferably, described y=0.5.
Preferably, described step 2) in, after the mixing of each solution, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C.
Preferably, described step 3) in, after passing into gaseous mixture, pre-burning 4h at 300～500 DEG C, finally it is calcined 24h at 700 DEG C.
Present invention also offers a kind of Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3The preparation method of magnesium cell anode material, described method comprises the steps:
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 70～80 DEG C, it is stirred vigorously 4～8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80～100 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 3～5h at 300～500 DEG C, finally it is calcined 20～26h at 700 DEG C, obtains black powder and be Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material;
Wherein, y=0.1～0.5.
Preferably, described y=0.5.
Preferably, described step 2) in, after the mixing of each solution, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C.
Preferably, described step 3) in, after passing into gaseous mixture, pre-burning 4h at 300～500 DEG C, finally it is calcined 24h at 700 DEG C.
Magnesium cell anode material prepared by present invention discharge capacity first can reach 205mAh/g, and capability retention is more than 90%, and most high energy reaches 96.1%.
Accompanying drawing explanation
Fig. 1 is that difference mixes the XRD figure of sample under nickel vanadium amount;
Detailed description of the invention
With detailed description of the invention, the present invention is further detailed explanation below.
Embodiment 1
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 70 DEG C, it is stirred vigorously 8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 100 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 5h at 500 DEG C, finally it is calcined 26h at 700 DEG C, obtains black powder and be Mg0.6(Ni0.05V0.05Ti0.9)2(PO4)3Magnesium cell anode material.
Embodiment 2
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 80 DEG C, it is stirred vigorously 4h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 5h at 300 DEG C, finally it is calcined 20h at 700 DEG C, obtains black powder and be Mg0.7(Ni0.1V0.1Ti0.8)2(PO4)3Magnesium cell anode material.
Embodiment 3
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 4h at 400 DEG C, finally it is calcined 24h at 700 DEG C, obtains black powder and be Mg0.8(Ni0.15V0.15Ti0.7)2(PO4)3Magnesium cell anode material.
Embodiment 4
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 78 DEG C, it is stirred vigorously 5h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 4h at 400 DEG C, finally it is calcined 24h at 700 DEG C, obtains black powder and be Mg0.9(Ni0.2V0.2Ti0.6)2(PO4)3Magnesium cell anode material.
Embodiment 5
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 4h at 400 DEG C, finally it is calcined 24h at 700 DEG C, obtains black powder and be Mg (Ni0.25V0.25Ti0.5)2(PO4)3Magnesium cell anode material.
Comparative example 1
Mg is prepared according to the method identical with the application0.5Ti2(PO4)3, carry out electric performance test.
Comparative example 2
Mg is prepared according to the method identical with the application0.5V2(PO4)3, carry out electric performance test.
Comparative example 3
Mg is prepared according to the method identical with the application0.5Ni2(PO4)3, carry out electric performance test.
Comparative example 4
Mg is prepared according to the method identical with the application0.5(V0.5Ti0.5)2(PO4)3, carry out electric performance test.
Comparative example 5
Mg is prepared according to the method identical with the application0.5(Ni0.5Ti0.5)2(PO4)3, carry out electric performance test.
Comparative example 6
Mg is prepared according to the method identical with the application0.5(V0.5Ni0.5)2(PO4)3, carry out electric performance test.
The sign of sample
The thing phase of synthetic material, Cu target (λ=0.154056nm), pipe pressure 20kV, pipe flow 40mA is analyzed with the X ' automatic X-ray diffractometer of PertPRO type (Holland produces). With MDIJade5.0 and Origin8.0, XRD data are analyzed and processed. Sample prepared by embodiment 1-5, adopting and the magnesium cell anode material of y=0.6 or 0.7 or 0.8 prepared by method that embodiment 3 is identical has carried out XRD test, result is as shown in Figure 1. The X-ray diffraction spectrum of respectively y=0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 in Fig. 1. It can be seen that during y=0.1～0.5, Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3The XRD diffraction pattern of magnesium cell anode material is substantially identical with the main peaks of base peak, when y=0.6～0.8, and Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3The XRD diffraction pattern of magnesium cell anode material has other impurity peaks; After by analysis, impurity component not can determine that. Therefore, when y is in 0.1～0.5 scope, Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material crystalline structure does not change, as y > 0.5 time, not clear impurity peaks occurs, crystalline structure is impacted.
Electric performance test
Embodiment 1-5 and comparative example 1-6 sample and the acetylene black prepared and polyvinylidene fluoride (PVDF) mixs by the mass ratio of 75:15:10 that to put into grinding in agate mortar uniform and add appropriate organic solvent NMP (N-Methyl pyrrolidone), after grinding to form homogeneous paste thing, being evenly applied on positive pole disk, at 95 DEG C, vacuum drying 4h obtains positive plate. In the glove box of full high-purity argon, with metal magnesium sheet for negative pole, microporous polypropylene membrane Celgard2400 is barrier film, with 0.25mol/LMg (AlCl2BuEt)2THF solution be electrolyte, be assembled into experimental cell, carry out charge and discharge cycles test, result is as shown in table 1.
The magnesium cell anode material electric performance test result that table 1 embodiment 1-5 and comparative example 1-6 prepares
As can be seen from the above table, the discharge capacity mixing the magnesium cell anode material after nickel vanadium increases along with the increase mixing nickel vanadium amount. Capability retention after 500 discharge cycles is more than 90%, and most high energy reaches 96.1%.
Claims (8)
1. a Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, described positive electrode is prepared from by following methods:
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 70～80 DEG C, it is stirred vigorously 4～8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80～100 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 3～5h at 300～500 DEG C, finally it is calcined 20～26h at 700 DEG C, obtains black powder and be Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material;
Wherein, y=0.1～0.5.
2. Mg according to claim 10.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, it is characterised in that described y=0.5.
3. Mg according to claim 10.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, it is characterised in that described step 2) in, after the mixing of each solution, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C.
4. Mg according to claim 10.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material, it is characterised in that described step 3) in, after passing into gaseous mixture, pre-burning 4h at 300～500 DEG C, finally it is calcined 24h at 700 DEG C.
5. a Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3The preparation method of magnesium cell anode material, described method comprises the steps:
1) by Mg:Ni:V:Ti:PO in gained magnesium cell anode material molecular formula4 3-Mol ratio, weigh MgCO3、(NH4)2HPO4, and nickel oxalate and NH4VO3, by MgCO3(NH4)2HPO4Being dissolved in deionized water, nickel oxalate is dissolved in ammonia, NH4VO3It is dissolved in hot water;
Weigh Ti (C4H9O)4, and in the ratio dehydrated alcohol of 1:4 by Ti (C4H9O)4Dissolve;
2) by step 1) each solution mixing of gained, at 70～80 DEG C, it is stirred vigorously 4～8h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 80～100 DEG C;
3) grinding of light yellow xerogel is placed in atmosphere tube type stove and passes into N2-H2Gaseous mixture, pre-burning 3～5h at 300～500 DEG C, finally it is calcined 20～26h at 700 DEG C, obtains black powder and be Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3Magnesium cell anode material;
Wherein, y=0.1～0.5.
6. method according to claim 5, it is characterised in that described y=0.5.
7. method according to claim 5, it is characterised in that described step 2) in, after the mixing of each solution, at 75 DEG C, it is stirred vigorously 6h so that it is dehydration generates yellow sol, is dried, obtains light yellow xerogel at 90 DEG C.
8. method according to claim 5, it is characterised in that described step 3) in, after passing into gaseous mixture, pre-burning 4h at 300～500 DEG C, finally it is calcined 24h at 700 DEG C.
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| CN102931403A (en) * | 2012-11-08 | 2013-02-13 | 上海交通大学 | Application method of titanium magnesium phosphate in anode material of chargeable magnesium battery |
| CN104108696A (en) * | 2014-07-14 | 2014-10-22 | 中国科学院青海盐湖研究所 | Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3 magnesium battery cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102931403A (en) * | 2012-11-08 | 2013-02-13 | 上海交通大学 | Application method of titanium magnesium phosphate in anode material of chargeable magnesium battery |
| CN104108696A (en) * | 2014-07-14 | 2014-10-22 | 中国科学院青海盐湖研究所 | Mg0.5+y(Ni0.5yV0.5yTi1-y)2(PO4)3 magnesium battery cathode material and preparation method thereof |
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