CN107293737A - A kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And preparation method - Google Patents

A kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And preparation method Download PDF

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CN107293737A
CN107293737A CN201710550127.4A CN201710550127A CN107293737A CN 107293737 A CN107293737 A CN 107293737A CN 201710550127 A CN201710550127 A CN 201710550127A CN 107293737 A CN107293737 A CN 107293737A
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magnesium ion
ion battery
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negative material
mgeu
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And preparation method, it is characterized in that：The negative material is structure of double perovskite, changes the crystallization property with lattice defect crystal using the electric field for applying specific direction in high temperature solid state reaction in preparation process, grows to form cylindrical shape particle along direction of an electric field；The non-homogeneous crystallization of cylindrical shape particle surface simultaneously and unevenly adhere to sintering aid at the big position of surface curvature radius and part adhesive turns into continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance and electromigration resistance；Improve the speed of magnesium ion transfer ability and redox reaction；Also there is certain structural rigidity, be that the material volume in charge and discharge process changes to form buffering；Further occupied jointly by the Mg and Eu of A and Eu positions Ca doping and the Cu of B, Zn doping so as to form high performance Magnesium ion battery negative material.

Description

A kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And prepare Method
Technical field
The present invention relates to a kind of Magnesium ion battery negative material manufacture method technical field.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of lithium ion battery plus-negative plate material is the primary goal of scientific and technical personnel's research, high power capacity both positive and negative polarity It is high-leveled and difficult to meet high power consumption and high power that the research and development of material can alleviate current Li-ion batteries piles volume big, heavy weight, price The situation that equipment needs.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hesitated all the time Wander between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.Compare In positive pole, the room for promotion of negative material capacity is also very big, such as tin and tin alloy material, silicon and silicon alloy material, all kinds of transition Metal oxide [Md.Arafat Rahman, Guangsheng Song, Anand I.Bhatt, Yat Choy Wong, and Cuie Wen, Nanostructured Silicon Anodes for High-Performance Lithium-Ion Batteries, Adv.Funct.Mater.2016,26,647-678] etc..But high rate performance, circulation such as to take into account material Capacity retention can be still extremely difficult.Wherein main cause has：1st, electrode material simultaneously will when occurring redox reaction Conducted with quick Lithium-ion embeding deintercalation and electronics, i.e., while there is good electron conduction and ionic conductivity, no Few negative material has higher lithium ion diffusion coefficient, but is electronic body, and the negative material also having is good Electronic conductor, but lithium ion diffusivity is weak, so that the polarization of battery is increased considerably；2nd, many electrode materials are in lithium Ion has larger Volume Changes during being embedded in deintercalation, so as to cause the broken and active electrode material of electrode material granules Expect the loss in cyclic process, big Volume Changes also bring material lattice transformation in charge and discharge process to produce the second phase simultaneously And have a strong impact on the performance of battery.3rd, the lithium cell negative pole material of conversion reaction mechanism, the electronic isolation of reaction product lithium compound Property has had a strong impact on the invertibity of material.
Because there is multielectron transfer in the lithium cell negative pole material of alloy mechanism and the lithium cell negative pole material of conversion reaction mechanism Process often shows higher specific capacity, and metal oxide, sulfide, phosphide, carbonate, chloride are used as allusion quotation in recent years The conversion alloy reaction mechanism lithium cell negative pole material of type is gradually of concern.With the work of conventional lithium ion battery electrode material Principle is different, traditional lithium ion cell positive and negative pole all exist lithium ion can be embedded in or deintercalation space, it is and electric Solve lithium ion in matter embedded back and forth and deintercalation and " rocking chair " proposed as Armand etc. that discharge between a positive electrode and a negative electrode Battery.And material is changed by taking+divalent metal oxide as an example, it may occur that similar following change：
2Li++MeO+2e-→Li2O+Me0
And after conversion reaction, it is also possible to can occur the alloy process of diversified forms, such as：
Lim+Me0 n→LimMe0 n
It can be discharged more than 1000mAh.g during the two-1Specific capacity, thus it is high to obtain investigation of materials personnel The attention of degree.But as it was previously stated, to take into account the high rate performance of material, circulation volume retention property still extremely difficult.Metal oxygen These conversion negative materials of compound, sulfide, phosphide, carbonate, chloride obtain more research, these conversion alloys Type negative material is all often single metallization compound.In addition, reserves of the elemental lithium in the earth's crust are very low, rare lithium resource causes Following lithium ion battery cost constantly rises.Seeking a kind of alternative inexpensive electrochemical energy storing device turns into urgently to be resolved hurrily The problem of.The electrochemical properties of magnesium are similar with lithium, and earth rich reserves, be it is following be expected to replace lithium ion battery most have uncommon The selection of prestige.
As lithium ion transition material, the Magnesium ion battery negative material of alloy mechanism is it can also happen that following electrification Learn reaction：
Mg2++MeO+2e-→MgO+Me0
Mgm+Me0 n→MgmMe0 n
And larger specific capacity can be discharged, but generally because magnesium ion ionic radius is larger, electrode potential is low, Migration velocity in electrode material is slow, and the battery performance such as energy density, power density still has very big compared with lithium ion battery Gap.And the negative pole candidate material of Magnesium ion battery is few, study it also very inadequate at present.
Perovskite structure ABO3Type oxide obtains important application in solar cells recently.Its structure is A The larger cation of radius, in 12 coordination structures, positioned in the hole that octahedron is constituted；B are transition metal class Compared with small cation, with six oxonium ion formation octahedral coordinations.Change A, the element species of B location, A, the element of B location by it His same valence state or the atomic component of aliovalent state are substituted all there may be different types of lattice defect, so as to as with The functional material of different functionalities.ABO3Type oxide can carry out alloy reaction when carrying out alloy reaction with two kinds of metals, its There may be the Alloy solid solution of a variety of phases, due to bimetallic interaction, it is also possible to produce completely different with monometallic Electrochemical properties, therefore ABO3Type oxide is likely to become a kind of high-performance Magnesium ion battery negative material, and it may be carried For near or above 300mAh.g-1Specific capacity, magnesium ion enter or abjection material volume change it is also smaller；But the material Research and development in Magnesium ion battery is substantially at blank.And its subject matter is：1st, ionic conductivity and electronic conductance Rate is relatively low；2nd, the product magnesia after conversion reaction is electronic body and its magnesium ion Diffusion Activation Energy is also higher, cause compared with Big activation polarization；3rd, synthesis temperature is higher, easily causes growing up and reuniting for crystal grain.
For these problems, these problems can be extenuated to a certain extent by changing the pattern of material, such as by of material Particle size reduction can reduce the approach of magnesium ion diffusion to the yardstick of nanometer, shorten the diffusion time of magnesium ion to improve material Dynamic performance；Too small granularity also easily causes the difficulty of electronic conduction between particle；Reunion between same particle or Excessive particle easily causes the infiltration of electrolyte between particles difficult, the problems such as magnesium ion migration velocity is slow；Ion doping It is also a kind of microstructure of effective regulation lattice, changes the means of lattice electron and ionic transport properties, however, ion is mixed Miscellaneous even polyion collaboration doping is extremely complex to the mechanism of action of parent, and effect is often difficult to expect.In addition using double calcium Perovskite like structure A and B can be occupied by two kinds of metals, partly can also be replaced by aliovalent or iso-valence metal, therefore, to material Expect the flexible adjustment of regulation and control, electronics and the ion motion property of structure.
Therefore it is structure of double perovskite oxidation to develop a kind of structure of double perovskite oxide with excellent electrochemical performance The key that thing is applied as secondary Magnesium ion battery negative material.
The content of the invention
The present invention proposes a kind of Magnesium ion battery negative material for existing background technology MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And preparation method, it is characterized in that：The negative material is structure of double perovskite, is prepared Change the crystallization property with lattice defect crystal using the electric field for applying specific direction in high temperature solid state reaction in journey, along electricity Field direction grows to form cylindrical shape particle；The non-homogeneous crystallization of cylindrical shape particle surface simultaneously and it is big in surface curvature radius Position unevenly adheres to sintering aid and part adhesive turns into continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance Power, improves locomitivity of the magnesium ion in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase With the contact area of electrolyte, accelerate electrolyte and the magnesium ion transfer ability and the speed of redox reaction in lattice；This The structure of sample also has certain structural rigidity, is that the material volume in charge and discharge process changes to form buffering；Further pass through A The Mg and Eu of position are occupied jointly, are improved electronic conductivity and are adulterated by the Ca of Eu positions, improve magnesium ion electrical conductivity；Pass through The Cu of B, Zn doping improve the stability of perovskite structure, ultimately form high performance Magnesium ion battery negative material.
This Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6, its preparation method is：By four hydrations Calcium nitrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, zinc nitrate hexahydrate, tungstic acid hydrate ammonium According to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours.By the material after ball milling in tube furnace with 2-10 DEG C/min Speed be warming up to after 800-900 DEG C tube furnace two ends apply a DC voltage, voltage is 600-900V, at this temperature and 30 DEG C are cooled to the furnace after being incubated 3-6 hours under electric field；Material after cooling is ground 5-15 minutes in mortar, in polytetrafluoro Ethene agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 900-1200rpm speed, metaboric acid The mass ratio of the quality of lithium saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 5-10 minutes, by constant temperature Temperature is reduced to 18-22 DEG C and continues stirring 5-15 minutes, filters thereafter, 5-10 is dried in 120-160 DEG C of drying box small When.Then dried material is warming up to 450-550 DEG C and at this temperature in tube furnace with 2-10 DEG C/min of speed Magnesium ion battery negative material MgEu is made in 3-5 hours in insulation0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
Compared with prior art, the advantage of the invention is that：Utilize the electricity for applying specific direction in high temperature solid state reaction Field changes the crystallization property with lattice defect crystal, grows to form cylindrical shape particle along direction of an electric field；While cylindrical shape The non-homogeneous crystallization of particle surface and unevenly adhere to sintering aid at the big position of surface curvature radius and part adhesive turns into Continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the magnesium ion in lattice；The company of being formed Continuous electron transfer network, reduces electromigration resistance；Increase and the contact area of electrolyte, accelerate in electrolyte and lattice The speed of magnesium ion transfer ability and redox reaction；Such structure also has certain structural rigidity, is discharge and recharge Material volume in journey changes to form buffering；Further occupied jointly by the Mg and Eu of A, improve electronic conductivity and lead to The Ca doping of portion Eu positions is crossed, magnesium ion electrical conductivity is improved；By the Cu of B, Zn doping improves the stability of perovskite structure, Ultimately form high performance Magnesium ion battery negative material.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 0.1V- 3.0V, charging and discharging currents 0.5C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, Zinc nitrate hexahydrate, tungstic acid hydrate ammonium are according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, ball The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling in tube furnace In with 10 DEG C/min of speed be warming up to after 900 DEG C tube furnace two ends apply a DC voltage, voltage is 900V, herein At a temperature of and electric field under insulation 5 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 12 minutes in mortar, poly- Tetrafluoroethene agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 1200rpm speed, metaboric acid The mass ratio of the quality of lithium saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 9 minutes, by thermostat temperature It is reduced to 22 DEG C and continues stirring 15 minutes, filters thereafter, dried 10 hours in 160 DEG C of drying box.Then after drying Material in tube furnace with 10 DEG C/min of speed be warming up to 550 DEG C and at this temperature be incubated 5 hours be made the magnesium ion Cell negative electrode material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
Embodiment 2：By calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, Zinc nitrate hexahydrate, tungstic acid hydrate ammonium are according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, ball The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 15 hours.By the material after ball milling in tube furnace In be warming up to 8 DEG C/min of speed after 900 DEG C and apply a DC voltage at the two ends of tube furnace, voltage is 900V, warm herein 30 DEG C are cooled to the furnace after being incubated 5 hours under degree and under electric field；Material after cooling is ground 12 minutes in mortar, poly- four PVF agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 1000rpm speed, lithium metaborate The mass ratio of the quality of saturated solution and the material after the cooling immersed is 10: 1, and after persistently stirring 7 minutes, thermostat temperature is dropped As little as 18 DEG C and continue stirring 10 minutes, filter thereafter, in 140 DEG C of drying box dry 8 hours.Then by dried thing Material is warming up to 500 DEG C and is incubated 4 hours at this temperature in tube furnace with 7 DEG C/min of speed is made the Magnesium ion battery Negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
Embodiment 3：By calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, Zinc nitrate hexahydrate, tungstic acid hydrate ammonium are according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, ball The mass ratio of mill and material is 20: 1, with 200 revs/min of speed ball milling 10 hours.By the material after ball milling in tube furnace In be warming up to 2 DEG C/min of speed after 800 DEG C and apply a DC voltage at the two ends of tube furnace, voltage is 600V, warm herein 30 DEG C are cooled to the furnace after being incubated 3 hours under degree and under electric field；Material after cooling is ground 6 minutes in mortar, poly- four PVF agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 900rpm speed, and lithium metaborate is satisfied It is 10: 1 with the quality of solution and the mass ratio of the material after the cooling of immersion, after persistently stirring 5 minutes, thermostat temperature is reduced To 20 DEG C and continue stirring 5 minutes, filter thereafter, in 120 DEG C of drying box dry 5 hours.Then by dried material 450 DEG C being warming up to 3 DEG C/min of speed in tube furnace and being incubated 3 hours obtained Magnesium ion batteries at this temperature bear Pole material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
Embodiment 4：By calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, Zinc nitrate hexahydrate, tungstic acid hydrate ammonium are according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, ball The mass ratio of mill and material is 20: 1, with 300 revs/min of speed ball milling 15 hours.By the material after ball milling in tube furnace In be warming up to 8 DEG C/min of speed after 850 DEG C and apply a DC voltage at the two ends of tube furnace, voltage is 900V, warm herein 30 DEG C are cooled to the furnace after being incubated 6 hours under degree and under electric field；Material after cooling is ground 15 minutes in mortar, poly- four PVF agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 1000rpm speed, lithium metaborate The mass ratio of the quality of saturated solution and the material after the cooling immersed is 10: 1, and after persistently stirring 7 minutes, thermostat temperature is dropped As little as 18 DEG C and continue stirring 5 minutes, filter thereafter, in 120 DEG C of drying box dry 5 hours.Then by dried thing Material is warming up to 520 DEG C and is incubated 5 hours at this temperature in tube furnace with 8 DEG C/min of speed is made the Magnesium ion battery Negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
Embodiment 5：By calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, Zinc nitrate hexahydrate, tungstic acid hydrate ammonium are according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, ball The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling in tube furnace In be warming up to 6 DEG C/min of speed after 850 DEG C and apply a DC voltage at the two ends of tube furnace, voltage is 800V, warm herein 30 DEG C are cooled to the furnace after being incubated 5 hours under degree and under electric field；Material after cooling is ground 12 minutes in mortar, poly- four PVF agitating paddle is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 1100rpm speed, lithium metaborate The mass ratio of the quality of saturated solution and the material after the cooling immersed is 10: 1, and after persistently stirring 7 minutes, thermostat temperature is dropped As little as 20 DEG C and continue stirring 12 minutes, filter thereafter, in 150 DEG C of drying box dry 7 hours.Then by dried thing Material is warming up to 500 DEG C and is incubated 5 hours at this temperature in tube furnace with 8 DEG C/min of speed is made the Magnesium ion battery Negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。

Claims (1)

1. a kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6Preparation method, it is characterized in that：By four Nitric hydrate calcium, magnesium nitrate hexahydrate, hafnium oxide, six nitric hydrate europiums, Gerhardite, zinc nitrate hexahydrate, hydration tungsten Sour ammonium is according to stoichiometric equation MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6It is put into ball mill, the mass ratio of ball milling and material For 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours；By the material after ball milling in tube furnace with 2-10 DEG C/ The speed of minute is warming up to after 800-900 DEG C applies a DC voltage at the two ends of tube furnace, and voltage is 600-900V, warm herein 30 DEG C are cooled to the furnace after being incubated 3-6 hours under degree and under electric field；Material after cooling is ground 5-15 minutes in mortar, Teflon stir oar is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 900-1200rpm speed, The mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 5-10 minutes, Thermostat temperature is reduced to 18-22 DEG C and continues stirring 5-15 minutes, filters thereafter, is dried in 120-160 DEG C of drying box 5-10 hours；Then dried material is warming up to 450-550 DEG C and herein in tube furnace with 2-10 DEG C/min of speed At a temperature of 3-5 hour obtained Magnesium ion battery negative material MgEu of insulation0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6。
CN201710550127.4A 2017-06-29 2017-06-29 A kind of Magnesium ion battery negative material MgEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6And preparation method Withdrawn CN107293737A (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘一帆 等: ""原料种类与煅烧温度对合成CaZrO3粉体的影响"", 《耐火材料》 *
李超: ""层状钙钛矿型Bi4Ti3O12铁电薄膜的择优取向生长与回线动力学标度"", 《中国优秀硕士论文全文数据库 工程科技I辑》 *

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