CN106972158A - A kind of continuous conduction original position C/Cu/CuF2Compound electric positive electrode of copper fluoride lithium and preparation method thereof - Google Patents

A kind of continuous conduction original position C/Cu/CuF2Compound electric positive electrode of copper fluoride lithium and preparation method thereof Download PDF

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Publication number
CN106972158A
CN106972158A CN201710213009.4A CN201710213009A CN106972158A CN 106972158 A CN106972158 A CN 106972158A CN 201710213009 A CN201710213009 A CN 201710213009A CN 106972158 A CN106972158 A CN 106972158A
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aqueous solution
copper
copper fluoride
lithium
original position
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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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 continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof; this method passes through the drying process under low temperature, high vacuum condition and the carbonization under gas shield and in-situ reducing process; form the continuous carbon film with hole and gap structure; and fixation forms copper fluoride and restores metallic copper in the surface in situ of copper fluoride particle on the carbon film, plays the electronic conductivity for increasing substantially composite；Homogeneity crystallization nuclei is provided in electric discharge for electrode material, the dynamics of reduction New phase formation hinders, and the side reaction products such as a variety of double salt of copper fluoride is generated in liquid phase reactor and with excellent chemical property while also avoid.

Description

A kind of continuous conduction original position C/Cu/CuF2The compound electric positive electrode of copper fluoride lithium and its system Preparation Method
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high-performance copper fluoride 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, Cosandey F, 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.Such as fluorination iron material has had many document reports, but often discharge curve does not have fluoride positive electrode There is obvious platform, average discharge volt is low, energy density and power ratio are relatively low, such as be fluorinated the averaged discharge current potential of iron material At 2.0 volts or so.But fluorination copper product has about 3.2V discharge platform voltage, all there is average voltage high and that capacity is big is excellent Point.But it is also considerably less as the report of anode material for lithium-ion batteries on fluorination copper product, main difficulty is that fluorination The chemical property of copper has close contact and poor repeatability with preparation process；Meanwhile, fluorination copper product is in organic electrolyte Stability is also inadequate；It also has a negative characteristic to be exactly that electronic conductivity is extremely low, therefore can cause in charge and discharge process Very high polarizing voltage, although have researcher and the electrical conductivity of material is improved using carbon black mixing and ball milling is added, but graininess Carbon black be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material is produced in electric discharge Raw metallic copper and lithium fluoride cenotype, cenotype small particles are kinetically being on a sticky wicket in the stage that originally forms, therefore to it Charge/discharge capacity afterwards, 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 copper fluoride material preparation method for having excellent electrochemical performance is to be fluorinated the key that copper product is applied as secondary cell.
The content of the invention
The present invention proposes continuous conduction original position C/Cu/CuF for existing background technology2Compound copper fluoride lithium ion battery Copper nitrate is fixed on holding by positive electrode and preparation method thereof, this method by the drying process under low temperature, high vacuum condition Copper product is fluorinated in the Continuous Polyacrylamide body of hole and gap structure and by liquid phase reactor in-situ preparation, is existed thereafter The Continuous Polyacrylamide with hole and gap structure is integrally transformed into hole and gap structure in heat treatment process Continuous carbon film, the continuous carbon film has high conductive capability, increases substantially the electronic conductivity of composite；Exist simultaneously Surface reduction in heat treatment process in copper fluoride particle goes out a certain amount of metallic copper, is provided for electrode material in electric discharge same Matter crystallization nuclei, the dynamics for reducing New phase formation hinders, and capacity, circulation volume stability and the electric discharge for improving material are flat Platform current potential.Pass through the immobilization of reaction raw materials, it is thus also avoided that the side reactions such as a variety of double salt of copper fluoride are generated in liquid phase reactor Product simultaneously has excellent chemical property.
This continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof, its It is characterized as：It is 5-15wt% copper nitrates, 6-12wt% acrylamides, 1-2wt%N, N to prepare composition '-methylene-bisacrylamide Starting aqueous solution, the quality of wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, uses polytetrafluoroethyl-ne Alkene agitating paddle is stirred 5-15 minutes with 900rpm-1200rpm speed.By the starting aqueous solution with 5-10 DEG C/min of speed Rise to 75-85 DEG C and keep the temperature to turn into gelatin gel until starting aqueous solution.The gel of formation is high in low temperature Dried in the environment of vacuum, gel can be put into cold by the drying process using finished product freeze drier in the market Start refrigeration machine in lyophilizer sample disc, treat that gelling temp is reduced to subzero 50 DEG C of subzero 45- in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 25-35Pa in system, baffle temperature control is opened and starts to dehydrate, its His operating parameter takes machine preset value, after stable gas pressure drying terminates in system, and it is full that material after drying is immersed into concentration With concentration 70-90%, the amount of ammonium fluoride material is the ammonium fluoride aqueous solution of 8-20 times of the amount of nitric acid copper material in starting aqueous solution In and in the case where Teflon stir oar is with 1000rpm-1200rpm speed stir 15-30 seconds, filter thereafter, in 80-120 DEG C drying box in dry 3-7 hours after 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 450-550 DEG C constant temperature is cooled down after 0.5-2 hours, prepares continuous conduction original position C/Cu/CuF2Compound copper fluoride lithium ion cell positive material Material.
Compared with prior art, the advantage of the invention is that：This method passes through dried under low temperature, high vacuum condition Journey, copper nitrate is fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and in situ by liquid phase reactor Generation fluorination copper product, thereafter integrally changes the Continuous Polyacrylamide with hole and gap structure in heat treatment process Into the continuous carbon film with hole and gap structure, the continuous carbon film has high conductive capability, increases substantially composite wood The electronic conductivity of material；The surface reduction in copper fluoride particle in heat treatment process goes out a certain amount of metallic copper simultaneously, is electricity Pole material electric discharge when provide homogeneity crystallization nuclei, reduce New phase formation dynamics hinder, improve material capacity, Circulation volume stability and discharge platform current potential.Pass through the immobilization of reaction raw materials, it is thus also avoided that fluorine is generated in liquid phase reactor Change the side reaction products such as a variety of double salt of copper and with excellent 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 5wt% copper nitrates, 6wt% acrylamides, 1wt%N, N to prepare composition '-methylene bisacrylamide acyl The starting aqueous solution of amine, is stirred 5 minutes using Teflon stir oar with 900rpm speed.By the starting aqueous solution with 5 DEG C/min speed rise to 75 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel.By the solidifying of formation Glue is dried in the environment of low-temperature high-vacuum degree, the finished product freeze drier that the drying process can be in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 45 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 25Pa in system, baffle temperature control is opened and starts to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 70%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 8 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle with 1000rpm speed stir 15 seconds, filter thereafter, in 80 DEG C of drying box dry 3 hours after 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 450 DEG C of constant temperature and cooled down after 0.5 hour, the company of preparing Continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 2：It is 15wt% copper nitrates, 12wt% acrylamides, 2wt%N, N to prepare composition '-methylene bisacrylamide The starting aqueous solution of acid amides, is stirred 15 minutes using Teflon stir oar with 1200rpm speed.By the starting aqueous solution 85 DEG C are risen to 10 DEG C/min of speed and keep the temperature to turn into gelatin gel until starting aqueous solution.It will be formed Gel in the environment of low-temperature high-vacuum degree dry, the finished product freeze drier that the drying process can be in the market, will Gel, which is put into freeze drier sample disc, starts refrigeration machine, treats that gelling temp is reduced to subzero 50 DEG C in sample disc, opens true Empty pump improves vacuum, treats that gas pressure is reduced to below 32Pa in system, opens baffle temperature control and starts to dehydrate, its His operating parameter takes machine preset value, after stable gas pressure drying terminates in system, and it is full that material after drying is immersed into concentration With concentration 90%, the amount of ammonium fluoride material be 18 times of the amount of nitric acid copper material in starting aqueous solution ammonium fluoride aqueous solution in and Teflon stir oar is filtered thereafter with being stirred 30 seconds under 1200rpm speed, is dried 7 hours in 120 DEG C of drying box Afterwards 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 550 DEG C of constant temperature 2 hours after cool down, prepare Continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 3：It is 7wt% copper nitrates, 9wt% acrylamides, 1.5wt%N, N to prepare composition '-methylene bisacrylamide The starting aqueous solution of acid amides, is stirred 10 minutes using Teflon stir oar with 1150rpm speed.By the starting aqueous solution 80 DEG C are risen to 7 DEG C/min of speed and keep the temperature to turn into gelatin gel until starting aqueous solution.By formation Gel is dried in the environment of low-temperature high-vacuum degree, and the drying process, will be solidifying using finished product freeze drier in the market Glue, which is put into freeze drier sample disc, starts refrigeration machine, treats that gelling temp is reduced to subzero 48 DEG C in sample disc, opens vacuum Pump improves vacuum, treats that gas pressure is reduced to below 30Pa in system, opens baffle temperature control and starts to dehydrate, other Operating parameter takes machine preset value, after stable gas pressure drying terminates in system, is saturation by material immersion concentration after drying Concentration 80%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 15 times of the amount of nitric acid copper material in starting aqueous solution and poly- Tetrafluoroethene agitating paddle is filtered thereafter with being stirred 25 seconds under 1100rpm speed, after being dried 5 hours in 100 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 500 DEG C of constant temperature 1 hour after cool down, the company of preparing Continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 4：It is 5wt% copper nitrates, 12wt% acrylamides, 2wt%N, N to prepare composition '-methylene bisacrylamide acyl The starting aqueous solution of amine, is stirred 8 minutes using Teflon stir oar with 1200rpm speed.By the starting aqueous solution with 8 DEG C/min speed rise to 82 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel.By the solidifying of formation Glue is dried in the environment of low-temperature high-vacuum degree, and the drying process is using finished product freeze drier in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 49 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 30Pa in system, baffle temperature control is opened and starts to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 85%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 20 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle with 1100rpm speed stir 25 seconds, filter thereafter, in 110 DEG C of drying box dry 7 hours after 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 500 DEG C of constant temperature and cooled down after 1.5 hours, the company of preparing Continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 5：It is 15wt% copper nitrates, 12wt% acrylamides, 2wt%N, N to prepare composition '-methylene bisacrylamide The starting aqueous solution of acid amides, is stirred 12 minutes using Teflon stir oar with 1100rpm speed.By starting aqueous solution with 10 DEG C/min of speed rises to 80 DEG C and keeps the temperature to turn into gelatin gel until starting aqueous solution.By formation Gel is dried in the environment of low-temperature high-vacuum degree, and the drying process, will be solidifying using finished product freeze drier in the market Glue, which is put into freeze drier sample disc, starts refrigeration machine, treats that gelling temp is reduced to subzero 46 DEG C in sample disc, opens vacuum Pump improves vacuum, treats that gas pressure is reduced to below 32Pa in system, opens baffle temperature control and starts to dehydrate, other Operating parameter takes machine preset value, after stable gas pressure drying terminates in system, is saturation by material immersion concentration after drying Concentration 85%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 16 times of the amount of nitric acid copper material in starting aqueous solution and poly- Tetrafluoroethene agitating paddle is filtered thereafter with being stirred 17 seconds under 1120rpm speed, after being dried 6 hours in 110 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 550 DEG C of constant temperature 2 hours after cool down, the company of preparing Continuous conduction original position C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.

Claims (1)

1. a kind of continuous conduction original position C/Cu/CuF2The preparation method of compound copper fluoride anode material for lithium-ion batteries, its feature For：Prepare composition be 5-15wt% copper nitrates, 6-12wt% acrylamides, 1-2wt%N, N '-methylene-bisacrylamide rise The quality of the beginning aqueous solution, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, is stirred using polytetrafluoroethylene (PTFE) Oar is mixed to stir 5-15 minutes with 900rpm-1200rpm speed；The starting aqueous solution is risen with 5-10 DEG C/min of speed To 75-85 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel；By the gel of formation in the market Finished product freeze drier on dry, gel is put into freeze drier sample disc and starts refrigeration machine, gel in sample disc is treated Temperature is reduced to subzero 50 DEG C of subzero 45-, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to 25-35Pa in system Hereinafter, open baffle temperature control to start to dehydrate, other operating parameters take machine preset value, treat stable gas pressure in system Dry after terminating, be saturated concentration 70-90% by material immersion concentration after drying, the amount of ammonium fluoride material is in starting aqueous solution With 1000rpm-1200rpm speed in the ammonium fluoride aqueous solution of 8-20 times of the amount of nitric acid copper material and in Teflon stir oar Degree lower stirring 15-30 seconds, is filtered thereafter, in 0.1% hydrogen and 99.9% after being dried 3-7 hours in 80-120 DEG C of drying box Argon gas it is mixed gas protected under be warming up to 450-550 DEG C of constant temperature and cooled down after 0.5-2 hours, prepare continuous conduction original position C/ Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
CN201710213009.4A 2017-03-25 2017-03-25 A kind of continuous conduction original position C/Cu/CuF2Compound electric positive electrode of copper fluoride lithium and preparation method thereof Withdrawn CN106972158A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344151A (en) * 2011-06-23 2012-02-08 中山大学 Prussian blue nano-scale hollow olivary microballoons

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344151A (en) * 2011-06-23 2012-02-08 中山大学 Prussian blue nano-scale hollow olivary microballoons

Non-Patent Citations (2)

* 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 *
张海波 等: ""聚丙烯酰胺的合成及应用研究进展"", 《高分子材料科学与工程》 *

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