CN106972160A - A kind of non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN106972160A
CN106972160A CN201710213060.5A CN201710213060A CN106972160A CN 106972160 A CN106972160 A CN 106972160A CN 201710213060 A CN201710213060 A CN 201710213060A CN 106972160 A CN106972160 A CN 106972160A
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bismuth
ammonium fluoride
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

A kind of non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, this method passes through the feed postition to the nitric hydrate bismuth of reaction raw materials five, the hybrid mode of ammonium fluoride and water, the design of addition speed, eliminate the addition for the dust technology for suppressing hydrolysis, it is to avoid dust technology has the risk for being acted on ammonium fluoride and producing high toxicity hydrogen fluoride；And the surface in situ in situ in fluorination bismuth particle restores a certain amount of high conductivity carbon and bismuth metal, bismuth metal provides homogeneity crystallization nuclei for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders；Such reaction mechanism mechanism of reaction also avoid the generation in liquid phase reactor and be fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.

Description

A kind of non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth lithium ion cell positive Material and preparation method thereof
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high-performance fluorination bismuth complex lithium.
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 anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years Come, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, screening Up to tens of kinds of the lithium ion cell positive gone out, but really have potential commercial applications prospect or be already present in the market just Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance It is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material capacity Circulate holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively 275mAh/g and 285mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And Progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, CosandeyF, Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10)： A1318-A1327.]：
nLi++MeFn+ne-→nLiF+Me0
It can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel The attention of degree.Wherein fluorination bismuth is due to there is about 7170WhL-1Volume and capacity ratio and have big advantage.Conventional fluorine Change the synthetic method of bismuth to be carried out with metal simple-substance with metal oxide/hydroxide or fluorine gas with hydrogen fluoride gas at high temperature Reaction, process conditions are harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares fluorination bismuth Then it can not often be used because by-products content is too high as positive electrode simultaneously because being hydrolyzed to suppress bismuth nitrate in water And the dust technology added has the risk for being acted on ammonium fluoride and producing high toxicity hydrogen fluoride.Bismuth is fluorinated as lithium ion secondary electricity Pond positive electrode also has a negative characteristic to be that its electronic conductivity is extremely low, therefore can cause in charge and discharge process very high Polarizing voltage.Although having researcher improves the electrical conductivity of material using carbon black mixing and ball milling is added, but granular charcoal It is black to be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material produces gold in electric discharge Belong to bismuth and lithium fluoride cenotype, cenotype small particles are kinetically being on a sticky wicket in the stage that originally forms, therefore to thereafter Charge/discharge capacity, discharge potential, the holding capacity of charge/discharge capacity can have a negative impact.
Therefore exploitation one kind has complete conductive link, purity height, technical process is environment-friendly, product quality is stable, tool The compound fluorination bismuth material preparation method for having excellent electrochemical performance is to be fluorinated the key that bismuth material is applied as secondary cell.
The content of the invention
The present invention proposes a kind of non-acid system liquid phase synthesis C/Bi/BiF for existing background technology3Compound fluorination bismuth lithium Ion battery positive electrode and preparation method thereof, this method passes through the mixing side to the nitric hydrate bismuth of reaction raw materials five, ammonium fluoride The feed postition of formula and water, the design for adding speed, eliminate the addition for the dust technology for suppressing hydrolysis, it is to avoid dust technology presence The risk for being acted on ammonium fluoride and producing high toxicity hydrogen fluoride；And the surface in situ in situ in fluorination bismuth particle is restored necessarily The high conductivity carbon and bismuth metal of amount, bismuth metal provide homogeneity crystallization nuclei for electrode material in electric discharge, reduce cenotype The dynamics of formation hinders, and improves capacity, circulation volume stability and the discharge platform current potential of material；Such reaction mechanism mechanism of reaction It also avoid the generation in liquid phase reactor and be fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.
This non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and its preparation side Method, it is characterized in that：The amount ratio of material is put into reactor for 1: 3 five nitric hydrate bismuths and ammonium fluoride, the reactor is not The hydrostatic column for steel matter of becoming rusty, the height of container and the ratio of diameter are 2-2.5: 1, volume of a container and five nitric hydrate bismuths Ratio with ammonium fluoride quality sum is 2-5L/Kg, when five nitric hydrate bismuths are less than or equal to 1Kg with ammonium fluoride quality sum, Volume of a container is 2 liters.5 circular flow entrances are set at the top of container, its center is respectively distributed to container circular top Center and mutually the angle of cut in 90 ° four radiuses midpoint, the 18-20% of its a diameter of container diameter.Five nitric hydrate bismuths and The mixture of ammonium fluoride is put into after reactor, the up-down vibration reactor, and the amplitude of vibration is 5-10 centimetres, and frequency is 1-3 times/ Second；Vibration stops vibration for 10-15 seconds, and from all fluid intakes of container top, with identical flow velocity, feeding polyethylene glycol is dense simultaneously Spend the aqueous solution for 0.1-0.3wt%, flow velocity be (volume of a container/5) × 0.3- (volume of a container/5) × 0.5L/ seconds until Volume full of container 80%.Thereafter using Teflon stir oar with 900rpm-1200rpm 5-15 points of speed stirring Clock, is filtered afterwards, in 0.1% hydrogen and the gaseous mixture of 99.9% argon gas after being dried 3-7 hours in 80-120 DEG C of drying box 400-480 DEG C of constant temperature is warming up under body protection to cool down after 0.5-2 hours, prepares non-acid system liquid phase synthesis C/Bi/BiF3 Compound fluorination bismuth anode material for lithium-ion batteries.
Compared with prior art, the advantage of the invention is that：This method passes through to the nitric hydrate bismuth of reaction raw materials five, fluorination The hybrid mode of ammonium and the feed postition of water, the design for adding speed, eliminate the addition for the dust technology for suppressing hydrolysis, it is to avoid Dust technology has the risk for being acted on ammonium fluoride and producing high toxicity hydrogen fluoride；And the surface in situ in situ in fluorination bismuth particle A certain amount of high conductivity carbon and bismuth metal are restored, bismuth metal provides homogeneity crystallization nuclei for electrode material in electric discharge, The dynamics for reducing New phase formation hinders, and improves capacity, circulation volume stability and the discharge platform current potential of material；So The reaction mechanism mechanism of reaction also avoid in liquid phase reactor the side reaction products such as a variety of double salt of generation fluorination bismuth and with excellent electricity Chemical property.
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 1.8V- 4.0V, charging and discharging currents 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：It is that five nitric hydrate bismuths and ammonium fluoride that 1: 3 gross mass is 1Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2: 1, volume of a container with The ratio of five nitric hydrate bismuths and ammonium fluoride quality sum is 2L/Kg.At the top of container, 5 circular flow entrances are set, its Center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, and its a diameter of container is straight The 18% of footpath.The mixture of five nitric hydrate bismuths and ammonium fluoride is put into after reactor, the up-down vibration reactor, the amplitude of vibration For 5 centimetres, frequency is 1 time/second；It is same with identical flow velocity from all fluid intakes of container top that vibration stops vibration after 10 seconds When feeding Polyethylene glycol be 0.1wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.3L/ seconds until full of container 80% volume.Thereafter stirred 5 minutes, filtered afterwards, at 80 DEG C with 900rpm speed using Teflon stir oar After being dried 3 hours in drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 400 DEG C of constant temperature 0.5 Cooled down after hour, prepare non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 2：It is that five nitric hydrate bismuths and ammonium fluoride that 1: 3 gross mass is 2Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.2: 1, volume of a container Ratio with five nitric hydrate bismuths and ammonium fluoride quality sum is 3L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 19% of diameter.The mixture of five nitric hydrate bismuths and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 7 centimetres, frequency is 2 times/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 12 seconds The aqueous solution that Polyethylene glycol is 0.2wt% is sent into simultaneously, and flow velocity is (volume of a container/5) × 0.5L/ seconds until full of appearance The volume of device 80%.Thereafter stirred 10 minutes, filtered afterwards, 100 with 1100rpm speed using Teflon stir oar DEG C drying box in dry 5 hours after 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 440 DEG C of constant temperature Cooled down after 1 hour, prepare non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 3：It is that five nitric hydrate bismuths and ammonium fluoride that 1: 3 gross mass is 3Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.5: 1, volume of a container Ratio with five nitric hydrate bismuths and ammonium fluoride quality sum is 5L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 20% of diameter.The mixture of five nitric hydrate bismuths and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 10 centimetres, frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds Speed simultaneously send into Polyethylene glycol be 0.3wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.4L/ seconds until full of The volume of container 80%.Thereafter stirred 15 minutes, filtered afterwards with 1200rpm speed using Teflon stir oar, After being dried 7 hours in 120 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 480 DEG C Constant temperature is cooled down after 2 hours, prepares non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth lithium ion cell positive material Material.
Embodiment 4：It is that five nitric hydrate bismuths and ammonium fluoride that 1: 3 gross mass is 1Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2: 1, volume of a container with The ratio of five nitric hydrate bismuths and ammonium fluoride quality sum is 2.5L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 18% of diameter.The mixture of five nitric hydrate bismuths and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 5 centimetres, frequency is 1 time/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 10 seconds The aqueous solution that Polyethylene glycol is 0.1wt% is sent into simultaneously, and flow velocity is (volume of a container/5) × 0.3L/ seconds until full of appearance The volume of device 80%.Thereafter stirred 10 minutes, filtered afterwards, 110 with 1150rpm speed using Teflon stir oar DEG C drying box in dry 5 hours after 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 420 DEG C of constant temperature Cooled down after 1 hour, prepare non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 5：It is that five nitric hydrate bismuths and ammonium fluoride that 1: 3 gross mass is 2Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.2: 1, volume of a container Ratio with five nitric hydrate bismuths and ammonium fluoride quality sum is 3L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 20% of diameter.The mixture of five nitric hydrate bismuths and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 10 centimetres, frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds Speed simultaneously send into Polyethylene glycol be 0.2wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.4L/ seconds until full of The volume of container 80%.Thereafter stirred 15 minutes, filtered afterwards with 1200rpm speed using Teflon stir oar, After being dried 5 hours in 120 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 460 DEG C Constant temperature is cooled down after 1.5 hours, prepares non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth lithium ion cell positive material Material.

Claims (1)

1. a kind of non-acid system liquid phase synthesis C/Bi/BiF3The preparation method of compound fluorination bismuth anode material for lithium-ion batteries, it is special Levy for：The amount ratio of material is put into reactor for 1: 3 five nitric hydrate bismuths and ammonium fluoride, the reactor is stainless steel Hydrostatic column, the height of container and the ratio of diameter are 2-2.5: 1, volume of a container and five nitric hydrate bismuths and ammonium fluoride The ratio of quality sum is 2-5L/Kg, when five nitric hydrate bismuths are less than or equal to 1Kg with ammonium fluoride quality sum, the body of container Product is 2 liters；Container top set 5 circular flow entrances, its center be respectively distributed to container circular top center and The midpoint of four radiuses of the mutual angle of cut in 90 °, the 18-20% of its a diameter of container diameter；Five nitric hydrate bismuths and ammonium fluoride Mixture is put into after reactor, the up-down vibration reactor, and the amplitude of vibration is 5-10 centimetres, and frequency is 1-3 times/second；Vibration After 10-15 seconds stop vibration from all fluid intakes of container top using identical flow velocity simultaneously send into Polyethylene glycol as The 0.1-0.3wt% aqueous solution, flow velocity be (volume of a container/5) × 0.3- (volume of a container/5) × 0.5L/ seconds until full of The volume of container 80%；Thereafter stirred 5-15 minutes with 900rpm-1200rpm speed using Teflon stir oar, it After filter, in the mixed gas protected of 0.1% hydrogen and 99.9% argon gas after being dried 3-7 hours in 80-120 DEG C of drying box Under be warming up to 400-480 DEG C of constant temperature and cooled down after 0.5-2 hours, prepare non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorine Change bismuth anode material for lithium-ion batteries.
CN201710213060.5A 2017-03-25 2017-03-25 A kind of non-acid system liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Withdrawn CN106972160A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931721A (en) * 2018-09-20 2020-03-27 丰田自动车株式会社 Active material and fluoride ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中南矿冶学院《冶金过程原理》编写小组: "《冶金过程原理》", 30 September 1973 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931721A (en) * 2018-09-20 2020-03-27 丰田自动车株式会社 Active material and fluoride ion battery
CN110931721B (en) * 2018-09-20 2023-02-28 丰田自动车株式会社 Active material and fluoride ion battery

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