CN106602040A - SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material and preparation method thereof - Google Patents

SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material and preparation method thereof Download PDF

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Publication number
CN106602040A
CN106602040A CN201710062462.XA CN201710062462A CN106602040A CN 106602040 A CN106602040 A CN 106602040A CN 201710062462 A CN201710062462 A CN 201710062462A CN 106602040 A CN106602040 A CN 106602040A
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nickel nitrate
sio
minutes
speed
nitrate hexahydrate
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方敏华
水淼
李月
陈超
李弯弯
舒杰
任元龙
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Ningbo University
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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

The invention discloses a SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material. The preparation process is as follows: coating SiO<2> on Co<2+>-Cu<2+> doped amorphous nickel nitrate particles in combination with a micro-emulsion and a spray-drying method, thereby resisting the erosion of an electrolyte; and then, under a high vacuum condition, removing crystallization water in a system by adopting a special heat treatment step to form the SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material. As Co<2+> is doped in the system, the electronic conductivity of the system is improved; with Cu<2+> ions, a Ni-O space structure is enabled to produce distortion and a lithium ion diffusion-migration channel is expanded so that the electric conductivity of lithium ions is improved; the particularly beneficial effect is that the material is amorphous and is isotropic, thereby being conductive to rapid conduction of the lithium ions; and thus, the overall electrochemical performance of nickel nitrate is greatly improved.

Description

A kind of SiO2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material and its system Preparation Method
Technical field
The present invention relates to a kind of compound lithium cell negative pole material manufacture method technical field of high-performance nickel nitrate.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation The definitely advantage such as life-span length, power density height, at present global portable power source market have more than 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 forms of energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, is to meet lasting electricity Power is in requisition for simultaneously using substantial amounts of energy-storage battery；The urban air-quality problem that vehicle exhaust brings is increasingly serious, electronic Instant 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 putting forward higher requirement to the performance of lithium ion battery.
The raising of the capacity of lithium ion battery plus-negative plate material be scientific and technical personnel research primary goal, 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 big current Li-ion batteries piles volume, 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, positive electrode specific capacity is low to have become the bottleneck for lifting lithium ion battery specific energy.Compare In positive pole, the room for promotion of negative material capacity is also very big, such as stannum and tin alloy material, silicon and aluminosilicate 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 such as to take into account the high rate performance of material, circulating Capacity retention can be still extremely difficult.Wherein main cause has：1st, when there is redox reaction in electrode material, while wanting Conduct with quick Lithium-ion embeding deintercalation and electronics, i.e., there is good electron conduction and ionic conductivity simultaneously, no Few negative material has higher lithium ion diffusion coefficient, but is but electronic body, so that the polarization of battery is significantly Degree increases；2nd, many electrode materials have larger change in volume during Lithium-ion embeding and deintercalation, so as to cause electrode Loss of the broken and active electrode material of material granule in cyclic process, big change in volume also brings discharge and recharge simultaneously Material lattice is changed in quality and produces the second phase and have a strong impact on the performance of battery in journey.3rd, the lithium cell negative pole material of conversion reaction mechanism, The electronic isolation of product lithium compound has had a strong impact on the reversibility of material.
The lithium cell negative pole material of alloy mechanism and the lithium cell negative pole material of conversion reaction mechanism often show higher ratio Capacity, in recent years metal-oxide, sulfide, phosphide, carbonate, chloride are negative as typical conversion reaction mechanism lithium electricity Pole material is gradually of concern.Different with the operation principle of conventional lithium ion battery electrode material, traditional lithium ion Anode and negative pole all exist lithium ion can be embedded in or deintercalation space, and the lithium ion in electrolyte is in positive pole and negative pole Between be embedded in back and forth and deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And material is changed with+divalent metal oxidation As a example by thing, it may occur that similar following change：
2Li++MeO+2e-→Li2O+Me0
Can discharge more than 1000mAh.g in this process-1Specific capacity, thus obtain investigation of materials personnel height Attention.But keep performance still extremely difficult as it was previously stated, taking into account the high rate performance of material, circulation volume.Metal is aoxidized Thing, sulfide, phosphide, carbonate, chloride these conversion negative materials obtain more research, and metal nitrate is produced The research and development of product is also considerably less at present.Nickel nitrate negative pole transition material can also be provided near or above 1000mAh.g-1's Specific capacity, and its multiplying power property is more superior than metal-oxide, sulfide, phosphide, carbonate, chloride, lithium ion is entered Or the material volume change of abjection is also less；And its subject matter is：1st, nickel nitrate contains compared with multi-crystallization water, and these are crystallized Shipwreck easily causes electrolyte decomposition to remove completely to the erosion of material surface and being partly dissolved for material itself；2nd, change Reacted product lithium nitrate is electronic body and its lithium ion Diffusion Activation Energy is also higher, causes very big electrochemistry pole Change；3rd, nitric acid nickel surface is unstable, is easily corroded by electrolyte.
Therefore it is that nitric acid nickel material is made to develop a kind of modified anhydrous nitric acid method for preparing nickel with excellent electrochemical performance For the key of serondary lithium battery negative material application.
The content of the invention
The present invention proposes a kind of SiO for existing background technology2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole Material and preparation method thereof, it is characterized by with reference to microemulsion and spray drying process in Co2+、Cu2+Doping amorphous nitric acid nickel particle Upper coated Si O2, resist the erosion of electrolyte；Then in high vacuum conditions, using in specific heat treatment step removal system Water of crystallization, formed SiO2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material；Co in system2+Doping raising system Electronic conductivity, Cu2+Ion causes Ni-O space structures to produce distortion, extends lithium ion diffusive migration passage, improves its lithium Ionic conductivity；It will be particularly beneficial that material is noncrystal, isotropism, be conducive to the quick conduction of lithium ion.So as to significantly Degree improves the comprehensive electrochemical of nickel nitrate.
This SiO2Cladding Co2+、Cu2+Adulterate amorphous nickel nitrate lithium cell negative pole material, and its preparation method is：Nitre is hydrated by six Sour nickel, the Gerhardite of amount 0.5-5% of Nickelous nitrate hexahydrate material, amount 0.5-5% of Nickelous nitrate hexahydrate material Cabaltous nitrate hexahydrate dissolving forms in deionized water total concentration of metal ions for 0.5-1.5molL-1Solution；The quality such as general The solution and hexamethylene mixing, add mixing after liquid quality percentage ratio for 0.5-3.0% CTAB, mixing after liquid quality Percentage ratio is the n-butyl alcohol of 0.1-1.0%, and after stirring 5-15 minutes with 500-900 rev/min of rotating speed 5-10 minutes are stood, its The tetraethyl orthosilicate for adding amount 0.5-5% of Nickelous nitrate hexahydrate material afterwards is stirred with 120-200 rev/min of rotating speed simultaneously 3-10 hours are stood after 2-5 minutes；Thereafter by the liquid system with 1-10mLmin-1Speed spraying is passed through by peristaltic pump The injection port of drying machine, other operating conditions are：Intake 0.5-3.5m3·min-1, 100 DEG C -130 DEG C of intake air temperature, go out 80 DEG C -95 DEG C of draught temperature；Tubular type is put into after the solid that collection is obtained is dried into 10-20 hours in 60 DEG C of -80 DEG C of drying baker In stove, extract air in tube furnace and be less than 0.5-3Pa to gas pressure, 75-95 DEG C is warmed up to simultaneously with 2-10 DEG C/min of speed 8-15 minutes are kept at this temperature and remain that pressure is less than 0.5-3Pa；Thereafter flow is passed through for 1-10Lmin-1Purity Higher than the argon of percent by volume 99.9%, and while 120-130 DEG C and here temperature are warmed up to 20-30 DEG C/min of speed Degree is lower to be kept for 5-15 minutes；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material.
Compared with prior art, it is an advantage of the current invention that：With reference to microemulsion and spray drying process in Co2+、Cu2+Mix Coated Si O in miscellaneous amorphous nitric acid nickel particle2, resist the erosion of electrolyte；Then in high vacuum conditions, at using specific heat Water of crystallization in reason step removal system, forms SiO2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material；In system Co2+Electronic conductivity, the Cu of doping raising system2+Ion causes Ni-O space structures to produce distortion, and extension lithium ion diffusion is moved Mobile Communication road, improves its lithium ion conductivity；It will be particularly beneficial that material is noncrystal, isotropism, be conducive to the fast of lithium ion Speed conduction.So as to increase substantially the comprehensive electrochemical of nickel nitrate.
Description of the drawings
The charging capacity of front 10 circulations of Fig. 1 materials, discharge capacity and efficiency for charge-discharge figure, voltage range 0.1V- 3.0V, charging and discharging currents 0.5C.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By Nickelous nitrate hexahydrate, the Gerhardite of the amount 0.5% of Nickelous nitrate hexahydrate material, six hydrations The cabaltous nitrate hexahydrate dissolving of the amount 0.5% of nickel nitrate material forms in deionized water total concentration of metal ions for 0.5mol L-1Solution；By etc. quality the solution and hexamethylene mixing, add mixing after liquid quality percentage ratio be 0.5% CTAB, Liquid quality percentage ratio is 0.1% n-butyl alcohol after mixing, and after stirring 5 minutes with 500 revs/min of rotating speed 5 minutes are stood, its The tetraethyl orthosilicate for adding the amount 0.5% of Nickelous nitrate hexahydrate material afterwards is stirred 2 minutes with 120 revs/min of rotating speed simultaneously Stand 3 hours afterwards；Thereafter by the liquid system with 1mLmin-1Speed the sample introduction of spray dryer is passed through by peristaltic pump Mouthful, other operating conditions are：Intake 0.5m3·min-1, 100 DEG C of intake air temperature, 80 DEG C of air outlet temperature；Collection is obtained Solid be dried 10 hours in 60 DEG C of drying baker after be put in tube furnace, extract air in tube furnace and be less than to gas pressure 0.5Pa, is warmed up to 75 DEG C and is kept for 8 minutes at this temperature and remain that pressure is less than 0.5Pa with 2 DEG C/min of speed； Thereafter flow is passed through for 1Lmin-1Purity is higher than the argon of percent by volume 99.9%, and while with 20 DEG C/min of speed It is warmed up to 120 DEG C and is kept for 5 minutes at this temperature；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole Material.
Embodiment 2：By Nickelous nitrate hexahydrate, the Gerhardite of the amount 5% of Nickelous nitrate hexahydrate material, six hydration nitre The cabaltous nitrate hexahydrate dissolving of the amount 5% of sour nickel material forms in deionized water total concentration of metal ions for 1.5molL-1's Solution；By etc. quality the solution and hexamethylene mixing, add mixing after liquid quality percentage ratio be 3.0% CTAB, mixing Afterwards liquid quality percentage ratio is 1.0% n-butyl alcohol, stands 10 minutes after stirring 15 minutes with 900 revs/min of rotating speed, thereafter Add the tetraethyl orthosilicate of the amount 5% of Nickelous nitrate hexahydrate material quiet stir 5 minutes with 200 revs/min of rotating speed simultaneously after Put 10 hours；Thereafter by the liquid system with 10mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, Other operating conditions are：Intake 3.5m3·min-1, 130 DEG C of intake air temperature, 95 DEG C of air outlet temperature；To collect what is obtained Solid is put in tube furnace after being dried 20 hours in 80 DEG C of drying baker, is extracted air in tube furnace and is less than 3Pa to gas pressure, 95 DEG C are warmed up to 10 DEG C/min of speed and kept for 15 minutes at this temperature and remain that pressure is less than 3Pa；Thereafter lead to Inbound traffics are 10Lmin-1Purity is higher than the argon of percent by volume 99.9%, and while is warmed up to 30 DEG C/min of speed 130 DEG C and at this temperature keep 15 minutes；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 3：By Nickelous nitrate hexahydrate, the Gerhardite of the amount 3% of Nickelous nitrate hexahydrate material, six hydration nitre The cabaltous nitrate hexahydrate dissolving of the amount 3% of sour nickel material forms in deionized water total concentration of metal ions for 1.0molL-1's Solution；By etc. quality the solution and hexamethylene mixing, add mixing after liquid quality percentage ratio be 1.0% CTAB, mixing Afterwards liquid quality percentage ratio is 0.5% n-butyl alcohol, stands 8 minutes after stirring 10 minutes with 600 revs/min of rotating speed, thereafter Add the tetraethyl orthosilicate of the amount 3% of Nickelous nitrate hexahydrate material quiet stir 4 minutes with 160 revs/min of rotating speed simultaneously after Put 6 hours；Thereafter by the liquid system with 6mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, its He is at operating condition：Intake 2.5m3·min-1, 120 DEG C of intake air temperature, 85 DEG C of air outlet temperature；By consolidating that collection is obtained Body is put in tube furnace after being dried 15 hours in 70 DEG C of drying baker, is extracted air in tube furnace and is less than 1Pa to gas pressure, with 6 DEG C/min of speed is warmed up to 85 DEG C and is kept for 12 minutes at this temperature and remain that pressure is less than 1Pa；Thereafter it is passed through Flow is 6Lmin-1Purity is higher than the argon of percent by volume 99.9%, and while is warmed up to 125 with 25 DEG C/min of speed DEG C and at this temperature keep 12 minutes；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 4：By Nickelous nitrate hexahydrate, the Gerhardite of the amount 5% of Nickelous nitrate hexahydrate material, six hydration nitre The cabaltous nitrate hexahydrate dissolving of the amount 0.5% of sour nickel material forms in deionized water total concentration of metal ions for 1.5molL-1 Solution；By etc. quality the solution and hexamethylene mixing, add liquid quality percentage ratio after mixing to be 2.0% CTAB, mixed Liquid quality percentage ratio is 0.6% n-butyl alcohol after conjunction, and after stirring 15 minutes with 700 revs/min of rotating speed 5 minutes are stood, its Add the tetraethyl orthosilicate of the amount 3% of Nickelous nitrate hexahydrate material to stir 4 minutes with 150 revs/min of rotating speed afterwards simultaneously after Stand 10 hours；Thereafter by the liquid system with 6mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, Other operating conditions are：Intake 2.5m3·min-1, 115 DEG C of intake air temperature, 80 DEG C of air outlet temperature；To collect what is obtained Solid is put in tube furnace after being dried 10 hours in 60 DEG C of drying baker, is extracted air in tube furnace and is less than to gas pressure 0.5Pa, is warmed up to 75 DEG C and is kept for 8 minutes at this temperature and remain that pressure is less than 0.5Pa with 2 DEG C/min of speed； Thereafter flow is passed through for 7Lmin-1Purity is higher than the argon of percent by volume 99.9%, and while with 20 DEG C/min of speed It is warmed up to 125 DEG C and is kept for 10 minutes at this temperature；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole Material.
Embodiment 5：By Nickelous nitrate hexahydrate, the Gerhardite of the amount 4% of Nickelous nitrate hexahydrate material, six hydration nitre The cabaltous nitrate hexahydrate dissolving of the amount 0.5% of sour nickel material forms in deionized water total concentration of metal ions for 1.2molL-1 Solution；By etc. quality the solution and hexamethylene mixing, add liquid quality percentage ratio after mixing to be 2.0% CTAB, mixed Liquid quality percentage ratio is 0.7% n-butyl alcohol after conjunction, and after stirring 15 minutes with 750 revs/min of rotating speed 5 minutes are stood, its The tetraethyl orthosilicate for adding the amount 3.5% of Nickelous nitrate hexahydrate material afterwards is stirred 4 minutes with 150 revs/min of rotating speed simultaneously Stand 10 hours afterwards；Thereafter by the liquid system with 8mLmin-1Speed the sample introduction of spray dryer is passed through by peristaltic pump Mouthful, other operating conditions are：Intake 2.5m3·min-1, 120 DEG C of intake air temperature, 80 DEG C of air outlet temperature；Collection is obtained Solid be dried 10 hours in 60 DEG C of drying baker after be put in tube furnace, extract air in tube furnace and be less than to gas pressure 0.8Pa, is warmed up to 75 DEG C and is kept for 8 minutes at this temperature and remain that pressure is less than 0.8Pa with 2 DEG C/min of speed； Thereafter flow is passed through for 7Lmin-1Purity is higher than the argon of percent by volume 99.9%, and while with 20 DEG C/min of speed It is warmed up to 125 DEG C and is kept for 10 minutes at this temperature；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole Material.

Claims (1)

1. a kind of SiO2Cladding Co2+、Cu2+The preparation method of doping amorphous nickel nitrate lithium cell negative pole material, it is characterized by by six water Close nickel nitrate, the Gerhardite of amount 0.5-5% of Nickelous nitrate hexahydrate material, amount 0.5- of Nickelous nitrate hexahydrate material 5% cabaltous nitrate hexahydrate dissolving forms in deionized water total concentration of metal ions for 0.5-1.5molL-1Solution；Will Mix etc. the solution and hexamethylene of quality, add liquid quality percentage ratio after mixing to be liquid after CTAB, the mixing of 0.5-3.0% Weight percentage ratio is the n-butyl alcohol of 0.1-1.0%, and after stirring 5-15 minutes with 500-900 rev/min of rotating speed 5-10 is stood Minute, the tetraethyl orthosilicate of amount 0.5-5% of Nickelous nitrate hexahydrate material is added thereafter simultaneously with 120-200 rev/min Rotating speed stands 3-10 hours after stirring 2-5 minutes；Thereafter by the liquid system with 1-10mLmin-1Speed pass through peristaltic pump The injection port of spray dryer is passed through, other operating conditions are：Intake 0.5-3.5m3·min-1, 100 DEG C of intake air temperature- 130 DEG C, 80 DEG C -95 DEG C of air outlet temperature；After the solid that collection is obtained is dried into 10-20 hours in 60 DEG C of -80 DEG C of drying baker In being put into tube furnace, extract air in tube furnace and be less than 0.5-3Pa to gas pressure, be warmed up to 2-10 DEG C/min of speed 75-95 DEG C and at this temperature keep 8-15 minutes and remain pressure be less than 0.5-3Pa；Thereafter flow is passed through for 1- 10L·min-1Purity is higher than the argon of percent by volume 99.9%, and while is warmed up to 120- with 20-30 DEG C/min of speed 130 DEG C and at this temperature keep 5-15 minutes；The SiO is obtained2Cladding Co2+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material Material.
CN201710062462.XA 2017-01-17 2017-01-17 SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material and preparation method thereof Pending CN106602040A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993147A (en) * 2015-06-08 2015-10-21 宁波大学 Method for preparing multilevel structure copper nitrate anode material
CN104993134A (en) * 2015-06-08 2015-10-21 宁波大学 Preparation method of lithium ion battery copper nitrate composite negative electrode material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993147A (en) * 2015-06-08 2015-10-21 宁波大学 Method for preparing multilevel structure copper nitrate anode material
CN104993134A (en) * 2015-06-08 2015-10-21 宁波大学 Preparation method of lithium ion battery copper nitrate composite negative electrode material

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