CN106803584A - A kind of liquid phase double-component coats Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material and preparation method thereof - Google Patents
A kind of liquid phase double-component coats Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material and preparation method thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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- 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
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- H—ELECTRICITY
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Abstract
A kind of liquid phase double-component coats Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material and preparation method, it is characterized by synthesizing Cu using solvent switch method2+、Cr3+Doping amorphous nickel nitrate simultaneously coats ZnO and TiO on its particle2, form double-component cladding Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material;Then in high vacuum conditions, using the crystallization water in specific heat treatment step removal system.ZnO claddings can increase substantially the electronic conduction ability of material;TiO2Cladding improves the ability that material resists electrolyte erosion;Cr in system3+Vacancy defect in the electronic conductivity and increase system of raising system of adulterating;Doping Cu2+Ion causes that Ni O space structures produce distortion, extends lithium ion diffusive migration passage, improves its lithium ion conductivity;It will be particularly beneficial that material is noncrystal, isotropism, be conducive to the quick conduction of lithium ion.So as to increase substantially the comprehensive electrochemical of nickel nitrate.
Description
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
Long lifespan, the power density definitely advantage such as high, 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 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 brings 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 requirement higher.
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 power consumption high 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 in 1991 is commercialized, 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 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
Conducted with quick Lithium-ion embeding deintercalation and electronics, i.e., there is good electron conduction and ionic conductivity simultaneously, no
Few negative material has lithium ion diffusion coefficient higher, but is but electronic body, so that the polarization of battery is significantly
Degree increases;2nd, many electrode materials have larger Volume Changes 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 Volume Changes also bring discharge and recharge simultaneously
Material lattice is changed in quality and produces the second performance for mutually having a strong impact on 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 invertibity of material.
The lithium cell negative pole material of alloy mechanism and the lithium cell negative pole material of conversion reaction mechanism often show ratio higher
Capacity, metal oxide, sulfide, phosphide, carbonate, chloride are negative as typical conversion reaction mechanism lithium electricity in recent years
Pole material is gradually of concern.Operation principle with conventional lithium ion battery electrode material is different, 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 embedded 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 highly
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 enters
Or the material volume change of abjection is also smaller;And its subject matter is:1st, nickel nitrate typically all contains compared with multi-crystallization water, and this
A little crystallizations water be difficult to remove completely and easily cause electrolyte decomposition to the erosion of material surface and material being partly dissolved in itself;
2nd, the product lithium nitrate after conversion reaction is electronic body and its lithium ion Diffusion Activation Energy is also higher, causes very big electrification
Learn polarization;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
It is the key of serondary lithium battery negative material application.
The content of the invention
The present invention proposes a kind of liquid phase double-component cladding Cu for existing background technology2+、Cr3+Doping amorphous nickel nitrate
Lithium cell negative pole material and preparation method, it is characterized by synthesizing Cu using solvent switch method2+、Cr3+Doping amorphous nickel nitrate and
ZnO and TiO is coated on its particle2, form double-component cladding Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material;Then exist
Under high vacuum condition, using the crystallization water in specific heat treatment step removal system.ZnO claddings can increase substantially material
Electronic conduction ability;TiO2Cladding improves the ability that material resists electrolyte erosion;Cr in system3+The electricity of raising system of adulterating
Vacancy defect in electron conductivity and increase system;Doping Cu2+Ion causes that Ni-O space structures produce distortion, extends lithium ion
Diffusive migration passage, improves its lithium ion conductivity;It will be particularly beneficial that material be noncrystal, isotropism, be conducive to lithium from
The quick conduction of son.So as to increase substantially the comprehensive electrochemical of nickel nitrate.
This liquid phase double-component coats Cu2+、Cr3+Adulterate amorphous nickel nitrate lithium cell negative pole material, and its preparation method is:Will
Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 0.5-5% of Nickelous nitrate hexahydrate material, the amount of Nickelous nitrate hexahydrate material
The Gerhardite of 0.5-5% forms total concentration of metal ions for 0.5-1.5molL in being dissolved in absolute ethyl alcohol-1Ethanol
Solution, by the solution with 15-30 drops min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, dropwise addition it is same
When be stirred with the speed of 1200-1500rpm with agitating paddle, 5-15 point is persistently stirred 5-15 minutes and stood after being added dropwise to complete
Clock, mixture I is referred to as by this mixture;The Zinc diacetate dihydrate of the amount 0.5-5% of Nickelous nitrate hexahydrate material is dissolved in nothing
It is 0.1-0.3molL that concentration is formed in water-ethanol-1Ethanol solution, by this solution with 20-60 drops min-1Speed instill
In mixture I, while being stirred to completion of dropping with the speed of 400-800rpm and standing 5-15 minutes;After this is stood
System is filtered, the solid matter and positive tetraethyl titanate, the 3- of solid matter mass of solid matter mass 0.5-5% for obtaining
10% ethanol, the deionized water of the 0.1-0.3% of solid matter mass are placed in ball mill, the mass ratio of ball milling and material
It is 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours, ball milling takes out material after finishing, in 60 DEG C of -80 DEG C of dryings
It is put into tube furnace after 10-20 hours is dried in case, air to gas pressure is less than 0.5-3Pa in extracting tube furnace, with 2-10
DEG C/min speed be warmed up to 75-95 DEG C and kept for 8-15 minute at this temperature and remain pressure less than 0.5-3Pa;
Thereafter flow is passed through for 1-10Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 20-30 DEG C/min
Speed be warmed up to 110-130 DEG C and at this temperature keep 5-15 minutes;Liquid phase double-component cladding Cu is obtained2+、Cr3+Mix
Miscellaneous amorphous nickel nitrate lithium cell negative pole material.
Compared with prior art, the advantage of the invention is that:Cu is synthesized using solvent switch method2+、Cr3+Doping amorphous
Nickel nitrate simultaneously coats ZnO and TiO on its particle2, form double-component cladding Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material
Material;Then in high vacuum conditions, using the crystallization water in specific heat treatment step removal system.ZnO claddings can be significantly
Improve the electronic conduction ability of material;TiO2Cladding improves the ability that material resists electrolyte erosion;Cr in system3+Doping is carried
Vacancy defect in the electronic conductivity and increase system of system high;Doping Cu2+Ion causes that Ni-O space structures produce distortion,
Extension lithium ion diffusive migration passage, improves its lithium ion conductivity;It will be particularly beneficial that material is noncrystal, isotropism,
Be conducive to the quick conduction of lithium ion.So as to increase substantially the comprehensive electrochemical of nickel nitrate.
Brief description of the drawings
The charging capacity of preceding 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 Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 0.5% of Nickelous nitrate hexahydrate material, six hydrations
The Gerhardite of the amount 0.5% of nickel nitrate material forms total concentration of metal ions for 0.5mol in being dissolved in absolute ethyl alcohol
L-1Ethanol solution, by the solution with 16 drop min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, drop
Plus while be stirred with the speed of 1300rpm with agitating paddle, persistently stirred after being added dropwise to complete 6 minutes and stand 6 minutes, will
This mixture is referred to as mixture I;The Zinc diacetate dihydrate of the amount 0.5% of Nickelous nitrate hexahydrate material is dissolved in absolute ethyl alcohol
Formation concentration is 0.1molL-1Ethanol solution, by this solution with 22 drop min-1Speed instill mixture I, while
It is stirred to completion of dropping with the speed of 400rpm and stands the system filtering by this after standing in 5 minutes, the solid that will be obtained
The positive tetraethyl titanate of material and the solid matter mass 0.5%, the 3% of solid matter mass ethanol, solid matter mass
0.1% deionized water be placed in ball mill, ball milling is 20: 1 with the mass ratio of material, with 200 revs/min of speed ball
Mill 12 hours, ball milling takes out material after finishing, and in being put into tube furnace after being dried 12 hours in 60 DEG C of drying boxes, extracts tube furnace
Middle air to gas pressure is less than 0.5Pa, is warmed up to 75 DEG C with 2 DEG C/min of speed and is kept for 8 minutes at this temperature and begun
Pressure is kept to be less than 0.5Pa eventually;Thereafter flow is passed through for 1Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and together
When with 20 DEG C/min of speed be warmed up to 110 DEG C and at this temperature keep 5 minutes;Liquid phase double-component cladding Cu is obtained2+、
Cr3+Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 2:By Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 1% of Nickelous nitrate hexahydrate material, six hydration nitre
The Gerhardite of the amount 1.5% of sour nickel material forms total concentration of metal ions for 1molL in being dissolved in absolute ethyl alcohol-1's
Ethanol solution, by the solution with 20 drop min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, dropwise addition
It is stirred with the speed of 1350rpm with agitating paddle simultaneously, is persistently stirred after being added dropwise to complete 7 minutes and stand 10 minutes, by this
Mixture is referred to as mixture I;The Zinc diacetate dihydrate of the amount 1.5% of Nickelous nitrate hexahydrate material is dissolved in shape in absolute ethyl alcohol
It is 0.2molL into concentration-1Ethanol solution, by this solution with 40 drop min-1Speed instill mixture I, while with
The speed of 600rpm is stirred to completion of dropping and stands 12 minutes;System filtering after this is stood, the solids for obtaining
The positive tetraethyl titanate of matter and the solid matter mass 2%, the 5% of solid matter mass ethanol, solid matter mass
0.2% deionized water is placed in ball mill, and ball milling is 20: 1 with the mass ratio of material, with 300 revs/min of speed ball milling
15 hours, ball milling took out material after finishing, in being put into tube furnace after being dried 15 hours in 70 DEG C of drying boxes, in extraction tube furnace
Air to gas pressure is less than 1Pa, and 85 DEG C and at this temperature holding 12 minutes and all the time are warmed up to 5 DEG C/min of speed
Pressure is kept to be less than 1Pa;Thereafter flow is passed through for 6Lmin-1Purity higher than percent by volume 99.9% argon gas, and simultaneously with
25 DEG C/min of speed is warmed up to 120 DEG C and is kept for 10 minutes at this temperature;Liquid phase double-component cladding Cu is obtained2+、Cr3+
Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 3:By Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 5% of Nickelous nitrate hexahydrate material, six hydration nitre
The Gerhardite of the amount 5% of sour nickel material forms total concentration of metal ions for 1.5molL in being dissolved in absolute ethyl alcohol-1's
Ethanol solution, by the solution with 30 drop min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, dropwise addition
It is stirred with the speed of 1500rpm with agitating paddle simultaneously, is persistently stirred after being added dropwise to complete 15 minutes and stand 15 minutes, by this
Mixture is referred to as mixture I;The Zinc diacetate dihydrate of the amount 4.5% of Nickelous nitrate hexahydrate material is dissolved in shape in absolute ethyl alcohol
It is 0.3molL into concentration-1Ethanol solution, by this solution with 55 drop min-1Speed instill mixture I, while with
The speed of 750rpm is stirred to completion of dropping and stands 15 minutes;System filtering after this is stood, the solids for obtaining
The positive tetraethyl titanate of matter and the solid matter mass 5%, the 9% of solid matter mass ethanol, solid matter mass
0.3% deionized water is placed in ball mill, and ball milling is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling
20 hours, ball milling took out material after finishing, in being put into tube furnace after being dried 15 hours in 70 DEG C of drying boxes, in extraction tube furnace
Air to gas pressure is less than 3Pa, and 90 DEG C and at this temperature holding 15 minutes and all the time are warmed up to 9 DEG C/min of speed
Pressure is kept to be less than 3Pa;Thereafter flow is passed through for 10Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously
130 DEG C are warmed up to 30 DEG C/min of speed and kept for 15 minutes at this temperature;Liquid phase double-component cladding Cu is obtained2+、
Cr3+Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 4:By Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 2% of Nickelous nitrate hexahydrate material, six hydration nitre
The Gerhardite of the amount 2.5% of sour nickel material forms total concentration of metal ions for 1.5molL in being dissolved in absolute ethyl alcohol-1
Ethanol solution, by the solution with 30 drop min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, be added dropwise
While be stirred with the speed of 1500rpm with agitating paddle, persistently stirred after being added dropwise to complete 10 minutes and stand 10 minutes, will
This mixture is referred to as mixture I;The Zinc diacetate dihydrate of the amount 2% of Nickelous nitrate hexahydrate material is dissolved in shape in absolute ethyl alcohol
It is 0.1molL into concentration-1Ethanol solution, by this solution with 60 drop min-1Speed instill mixture I, while with
The speed of 500rpm is stirred to completion of dropping and stands 12 minutes;System filtering after this is stood, the solids for obtaining
The positive tetraethyl titanate of matter and the solid matter mass 0.8%, the 3% of solid matter mass ethanol, solid matter mass
0.3% deionized water is placed in ball mill, and ball milling is 20: 1 with the mass ratio of material, with 230 revs/min of speed ball milling
10 hours, ball milling took out material after finishing, in being put into tube furnace after being dried 15 hours in 80 DEG C of drying boxes, in extraction tube furnace
Air to gas pressure is less than 2Pa, and 90 DEG C and at this temperature holding 15 minutes and all the time are warmed up to 8 DEG C/min of speed
Pressure is kept to be less than 2Pa;Thereafter flow is passed through for 8Lmin-1Purity higher than percent by volume 99.9% argon gas, and simultaneously with
30 DEG C/min of speed is warmed up to 130 DEG C and is kept for 10 minutes at this temperature;Liquid phase double-component cladding Cu is obtained2+、Cr3+
Doping amorphous nickel nitrate lithium cell negative pole material.
Embodiment 5:By Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 5% of Nickelous nitrate hexahydrate material, six hydration nitre
The Gerhardite of the amount 1% of sour nickel material forms total concentration of metal ions for 1.2molL in being dissolved in absolute ethyl alcohol-1's
Ethanol solution, by the solution with 15 drop min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, dropwise addition
It is stirred with the speed of 1200rpm with agitating paddle simultaneously, is persistently stirred after being added dropwise to complete 5 minutes and stand 10 minutes, by this
Mixture is referred to as mixture I;The Zinc diacetate dihydrate of the amount 2% of Nickelous nitrate hexahydrate material is dissolved in absolute ethyl alcohol and is formed
Concentration is 0.2molL-1Ethanol solution, by this solution with 40 drop min-1Speed instill mixture I, while with
The speed of 600rpm is stirred to completion of dropping and stands 10 minutes;System filtering after this is stood, the solids for obtaining
The positive tetraethyl titanate of matter and the solid matter mass 2%, the 3% of solid matter mass ethanol, solid matter mass
0.1% deionized water is placed in ball mill, and ball milling is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling
12 hours, ball milling took out material after finishing, in being put into tube furnace after being dried 15 hours in 80 DEG C of drying boxes, in extraction tube furnace
Air to gas pressure is less than 1Pa, and 85 DEG C and at this temperature holding 12 minutes and all the time are warmed up to 6 DEG C/min of speed
Pressure is kept to be less than 1Pa;Thereafter flow is passed through for 5Lmin-1Purity higher than percent by volume 99.9% argon gas, and simultaneously with
20 DEG C/min of speed is warmed up to 110 DEG C and is kept for 5 minutes at this temperature;Liquid phase double-component cladding Cu is obtained2+、Cr3+
Doping amorphous nickel nitrate lithium cell negative pole material.
Claims (1)
1. a kind of liquid phase double-component coats Cu2+、Cr3+The preparation process of doping amorphous nickel nitrate lithium cell negative pole material, it is characterized by:
By Nickelous nitrate hexahydrate, the Chromium nitrate (Cr(NO3)3),nonahydrate of the amount 0.5-5% of Nickelous nitrate hexahydrate material, Nickelous nitrate hexahydrate material amount
The Gerhardite of 0.5-5% forms total concentration of metal ions for 0.5-1.5molL in being dissolved in absolute ethyl alcohol-1Ethanol
Solution, by the solution with 15-30 drops min-1Speed be added dropwise in the toluene with the quality such as the ethanol solution, dropwise addition it is same
When be stirred with the speed of 1200-1500rpm with agitating paddle, 5-15 point is persistently stirred 5-15 minutes and stood after being added dropwise to complete
Clock, mixture I is referred to as by this mixture;The Zinc diacetate dihydrate of the amount 0.5-5% of Nickelous nitrate hexahydrate material is dissolved in nothing
It is 0.1-0.3molL that concentration is formed in water-ethanol-1Ethanol solution, by this solution with 20-60 drops min-1Speed instill
In mixture I, while being stirred to completion of dropping with the speed of 400-800rpm and standing 5-15 minutes;After this is stood
System is filtered, the solid matter and positive tetraethyl titanate, the 3- of solid matter mass of solid matter mass 0.5-5% for obtaining
10% ethanol, the deionized water of the 0.1-0.3% of solid matter mass are placed in ball mill, the mass ratio of ball milling and material
It is 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours, ball milling takes out material after finishing, in 60 DEG C of -80 DEG C of dryings
It is put into tube furnace after 10-20 hours is dried in case, air to gas pressure is less than 0.5-3Pa in extracting tube furnace, with 2-10
DEG C/min speed be warmed up to 75-95 DEG C and kept for 8-15 minute at this temperature and remain pressure less than 0.5-3Pa;
Thereafter flow is passed through for 1-10Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 20-30 DEG C/min
Speed be warmed up to 110-130 DEG C and at this temperature keep 5-15 minutes;Liquid phase double-component cladding Cu is obtained2+、Cr3+Mix
Miscellaneous amorphous nickel nitrate lithium cell negative pole material.
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Citations (2)
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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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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (1)
Title |
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XI ZHENG ETAL: ""Improved electrochemical property ofcopper nitrate hydrate by multiwall carbon nanotube"", 《ELECTROCHIMICA ACTA》 * |
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