CN106848304A - A kind of double-component coats Ni2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material and preparation method thereof - Google Patents
A kind of double-component coats Ni2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material and preparation method thereof Download PDFInfo
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Abstract
A kind of double-component coats Ni2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material and preparation method, the method combination microemulsion and spray drying process are in Ni2+、Cu2+Coated Si O on doping amorphous nitric acid cobalt granule2And ZnO layer, resist the erosion of electrolyte and improve the electronic conduction ability of material；Then in high vacuum conditions, using the crystallization water in specific heat treatment step removal system, double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material.Doping Ni in system2+、Cu2+Ion causes that Co 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 cobalt 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 cobalt 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.Cobalt 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, cobalt 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, cobalt nitrate surface is unstable, is easily corroded by electrolyte.
Therefore it is that cobalt nitrate material is made to develop a kind of modified anhydrous nitric acid cobalt preparation method 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 double-component cladding Ni for existing background technology2+、Cu2+Doping amorphous cobalt nitrate lithium electricity
Negative material and preparation method, the method combination microemulsion and spray drying process are in Ni2+、Cu2+Doping amorphous nitric acid cobalt granule
Upper coated Si O2And ZnO layer, resist the erosion of electrolyte and improve the electronic conduction ability of material；Then in high vacuum condition
Under, using the crystallization water in specific heat treatment step removal system, form double-component cladding Ni2+、Cu2+Doping amorphous nitric acid
Cobalt lithium cell negative pole material.Doping Ni in system2+、Cu2+Ion causes that Co-O space structures produce distortion, and extension lithium ion expands
Migrating channels are dissipated, its lithium ion conductivity is improved；It will be particularly beneficial that material is noncrystal, isotropism, be conducive to lithium ion
Quick conduction.So as to increase substantially the comprehensive electrochemical of cobalt nitrate.
This double-component coats Ni2+、Cu2+Adulterate amorphous cobalt nitrate lithium cell negative pole material, and its preparation method is：By six water
Close cobalt nitrate, the Gerhardite of the amount 0.5-5% of cabaltous nitrate hexahydrate material, the amount 0.5- of cabaltous nitrate hexahydrate material
5% Nickelous nitrate hexahydrate dissolving forms total concentration of metal ions for 0.5-1.5molL in deionized water-1Solution；Will
The solution and hexamethylene etc. quality mix, and liquid quality percentage is liquid after CTAB, the mixing of 0.5-3.0% after adding mixing
Weight percentage is the n-butanol of 0.1-1.0%, and 5-10 is stood after being stirred 5-15 minutes with 500-900 revs/min of rotating speed
Minute, the tetraethyl orthosilicate of amount 0.5-5% of cabaltous nitrate hexahydrate material is added thereafter simultaneously with 120-200 revs/min
Rotating speed stands 3-10 hours after stirring 2-5 minutes；By the solution 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；The titanate coupling agent of the solid and solid masses percentage 0.2-0.8% for obtaining will be collected, consolidated
The Zinc diacetate dihydrate of weight percentage 0.5-5%, the glycerine of solid masses percentage 0.2-1% and hexamethylene are with volume
Than being put into ball mill after the mixing liquid mixing for 1: 1, ball milling is 20: 1 with the mass ratio of material, with 200-400 revs/min
Speed ball milling 10-20 hours, ball milling takes out material after finishing, and is put into after drying 10-20 hours in 60 DEG C of -80 DEG C of drying boxes
In tube furnace, air to gas pressure is less than 0.5-3Pa in extracting tube furnace, and 75-95 is warmed up to 2-10 DEG C/min of speed
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-1
Purity higher than percent by volume 99.9% argon gas, and simultaneously with 20-30 DEG C/min of speed be warmed up to 120-130 DEG C and
Kept for 5-15 minutes at a temperature of this；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material.
Titanate coupling agent in preparation method as described above is isopropyl three (dioctyl pyrophosphate) titanate esters, two
(dioctyl pyrophosphoryl base) closes the one kind in fluoroacetic acid ester titanium, tetra isopropyl two (phosphorous acid dilauryl) titanate esters.
Compared with prior art, the advantage of the invention is that：With reference to microemulsion and spray drying process in Ni2+、Cu2+Mix
Coated Si O on miscellaneous amorphous nitric acid cobalt granule2And ZnO layer, resist the erosion of electrolyte and improve the electronic conduction ability of material；And
Afterwards in high vacuum conditions, using the crystallization water in specific heat treatment step removal system, double-component cladding Ni is obtained2+、Cu2 +Doping amorphous cobalt nitrate lithium cell negative pole material.Doping Ni in system2+、Cu2+Ion causes that Co-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 cobalt 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 cabaltous nitrate hexahydrate, the Gerhardite of the amount 0.5% of cabaltous nitrate hexahydrate material, six hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 0.5% of cobalt nitrate material forms total concentration of metal ions for 0.5mol in deionized water
L-1Solution；By etc. quality the solution and hexamethylene mix, add mixing after liquid quality percentage be 0.5% CTAB,
Liquid quality percentage is 0.1% n-butanol after mixing, and 5 minutes are stood after being stirred 5 minutes with 500 revs/min of rotating speed, its
The tetraethyl orthosilicate of the amount 0.5% of cabaltous nitrate hexahydrate material is added to be stirred 2 minutes with 120 revs/min of rotating speed simultaneously afterwards
Stand 3 hours afterwards；By the solution with 1mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other behaviour
It is as condition：Intake 0.5m3·min-1, 100 DEG C of intake air temperature, 80 DEG C of air outlet temperature；To collect the solid that obtains with
Isopropyl three (dioctyl pyrophosphate) titanate esters of solid masses percentage 0.2%, two hydrations of solid masses percentage 0.5%
Zinc acetate, the glycerine of solid masses percentage 0.2% and hexamethylene are put into ball after mixing as 1: 1 mixing liquid with volume ratio
Grinding machine, ball milling is 20: 1 with the mass ratio of material, and with 200 revs/min of speed ball milling 10 hours, ball milling finishes rear extract
Material, in being put into tube furnace after being dried 10 hours in 60 DEG C of drying boxes, air to gas pressure is less than in extracting tube furnace
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 gas of percent by volume 99.9%, and simultaneously with 20 DEG C/min of speed
It is warmed up to 120 DEG C and is kept for 5 minutes at this temperature；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate lithium electricity is negative
Pole material.
Embodiment 2：By cabaltous nitrate hexahydrate, the Gerhardite of the amount 3% of cabaltous nitrate hexahydrate material, six hydration nitre
The Nickelous nitrate hexahydrate dissolving of the amount 3% of sour cobalt material forms total concentration of metal ions for 1.2molL in deionized water-1's
Solution；By etc. quality the solution and hexamethylene mix, add mixing after liquid quality percentage be 2.0% CTAB, mixing
Liquid quality percentage is 0.8% n-butanol afterwards, stands 7 minutes after being stirred 12 minutes with 700 revs/min of rotating speed, thereafter
Add the tetraethyl orthosilicate of the amount 3.0% of cabaltous nitrate hexahydrate material to be stirred 4 minutes with 170 revs/min of rotating speed simultaneously after
Stand 7 hours；By the solution with 7mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 2.0m3·min-1, 120 DEG C of intake air temperature, 85 DEG C of air outlet temperature；To collect the solid that obtains with it is solid
Isopropyl three (dioctyl pyrophosphate) titanate esters of weight percentage 0.6%, two hydration acetic acid of solid masses percentage 3%
Zinc, the glycerine of solid masses percentage 0.6% and hexamethylene are put into ball milling after mixing as 1: 1 mixing liquid with volume ratio
Machine, ball milling is 20: 1 with the mass ratio of material, and with 300 revs/min of speed ball milling 15 hours, ball milling finishes rear extract
Material, in being put into tube furnace after being dried 15 hours in 70 DEG C of drying boxes, air to gas pressure is less than in extracting tube furnace
2.0Pa, is warmed up to 85 DEG C and is kept for 12 minutes at this temperature and remain that pressure is less than with 7 DEG C/min of speed
2.0Pa；Thereafter flow is passed through for 6Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 25 DEG C/min
Speed be warmed up to 125 DEG C and at this temperature keep 12 minutes；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous nitric acid
Cobalt lithium cell negative pole material.
Embodiment 3：By cabaltous nitrate hexahydrate, the Gerhardite of the amount 5% of cabaltous nitrate hexahydrate material, six hydration nitre
The Nickelous nitrate hexahydrate dissolving of the amount 5% of sour cobalt material forms total concentration of metal ions for 1.5molL in deionized water-1's
Solution；By etc. quality the solution and hexamethylene mix, add mixing after liquid quality percentage be 3.0% CTAB, mixing
Liquid quality percentage is 1.0% n-butanol afterwards, stands 10 minutes after being stirred 15 minutes with 900 revs/min of rotating speed, thereafter
Add the tetraethyl orthosilicate of the amount 5% of cabaltous nitrate hexahydrate material quiet stirred 5 minutes with 200 revs/min of rotating speed simultaneously after
Put 10 hours；By the solution with 10mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 3.5m3·min-1, 130 DEG C of intake air temperature, 95 DEG C of air outlet temperature；To collect the solid that obtains with it is solid
Two (dioctyl pyrophosphoryl bases) of weight percentage 0.8% close two hydration vinegar of fluoroacetic acid ester titanium, solid masses percentage 5%
Sour zinc, the glycerine of solid masses percentage 1% and hexamethylene are put into ball milling after mixing as 1: 1 mixing liquid with volume ratio
Machine, ball milling is 20: 1 with the mass ratio of material, and with 400 revs/min of speed ball milling 20 hours, ball milling finishes rear extract
Material, in being put into tube furnace after being dried 20 hours in 80 DEG C of drying boxes, air to gas pressure is less than 3Pa in extracting tube furnace,
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 and is warmed up to 30 DEG C/min of speed simultaneously higher than the argon gas of percent by volume 99.9%
130 DEG C and at this temperature keep 15 minutes；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material
Material.
Embodiment 4：By cabaltous nitrate hexahydrate, the Gerhardite of the amount 0.9% of cabaltous nitrate hexahydrate material, six hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 1.0% of cobalt nitrate material forms total concentration of metal ions for 1.5mol in deionized water
L-1Solution；By etc. quality the solution and hexamethylene mix, add mixing after liquid quality percentage be 3.0% CTAB,
Liquid quality percentage is 1.0% n-butanol after mixing, and 7 minutes are stood after being stirred 12 minutes with 800 revs/min of rotating speed,
Thereafter the tetraethyl orthosilicate of the amount 0.9% of cabaltous nitrate hexahydrate material is added to stir 4 points with 180 revs/min of rotating speed simultaneously
8 hours are stood after clock；By the solution with 8mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other
Operating condition is：Intake 2.5m3·min-1, 120 DEG C of intake air temperature, 90 DEG C of air outlet temperature；The solid for obtaining will be collected
With two (dioctyl pyrophosphoryl bases) of solid masses percentage 0.6% close fluoroacetic acid ester titanium, solid masses percentage 0.9% two
Hydration zinc acetate, the glycerine of solid masses percentage 0.8% and hexamethylene are put after being mixed as 1: 1 mixing liquid with volume ratio
Enter ball mill, ball milling is 20: 1 with the mass ratio of material, with 300 revs/min of speed ball milling 15 hours, ball milling takes after finishing
Go out material, in being put into tube furnace after being dried 15 hours in 70 DEG C of drying boxes, air to gas pressure is less than in extracting tube furnace
2.5Pa, is warmed up to 80 DEG C and is kept for 10 minutes at this temperature and remain that pressure is less than with 8 DEG C/min of speed
2.5Pa；Thereafter flow is passed through for 8Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 25 DEG C/min
Speed be warmed up to 120 DEG C and at this temperature keep 5 minutes；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate
Lithium cell negative pole material.
Embodiment 5：By cabaltous nitrate hexahydrate, the Gerhardite of the amount 0.5% of cabaltous nitrate hexahydrate material, six hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 5% of cobalt nitrate material forms total concentration of metal ions for 1.5molL in deionized water-1
Solution；By etc. quality the solution and hexamethylene mix, it is 0.5% CTAB, mixed to add liquid quality percentage after mixing
Liquid quality percentage is 1.0% n-butanol after conjunction, and 7 minutes are stood after being stirred 15 minutes with 900 revs/min of rotating speed, its
The tetraethyl orthosilicate of the amount 0.5% of cabaltous nitrate hexahydrate material is added to be stirred 4 minutes with 150 revs/min of rotating speed simultaneously afterwards
Stand 7 hours afterwards；By the solution with 7mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other behaviour
It is as condition：Intake 2.5m3·min-1, 130 DEG C of intake air temperature, 95 DEG C of air outlet temperature；To collect the solid that obtains with
Tetra isopropyl two (phosphorous acid dilauryl) titanate esters, the two of solid masses percentage 0.5% of solid masses percentage 0.2%
Hydration zinc acetate, the glycerine of solid masses percentage 0.2% and hexamethylene are put after being mixed as 1: 1 mixing liquid with volume ratio
Enter ball mill, ball milling is 20: 1 with the mass ratio of material, with 200 revs/min of speed ball milling 15 hours, ball milling takes after finishing
Go out material, in being put into tube furnace after being dried 15 hours in 75 DEG C of drying boxes, air to gas pressure is less than in extracting tube furnace
0.5Pa, is warmed up to 80 DEG C and is kept for 10 minutes at this temperature and remain that pressure is less than with 5 DEG C/min of speed
0.5Pa；Thereafter flow is passed through for 7Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 20 DEG C/min
Speed be warmed up to 120 DEG C and at this temperature keep 8 minutes；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate
Lithium cell negative pole material.
Claims (2)
1. a kind of double-component coats Ni2+、Cu2+Adulterate the preparation method of amorphous cobalt nitrate lithium cell negative pole material, it is characterized by by six
Nitric hydrate cobalt, the Gerhardite of the amount 0.5-5% of cabaltous nitrate hexahydrate material, the amount 0.5- of cabaltous nitrate hexahydrate material
5% Nickelous nitrate hexahydrate dissolving forms total concentration of metal ions for 0.5-1.5molL in deionized water-1Solution；Will
The solution and hexamethylene etc. quality mix, and liquid quality percentage is liquid after CTAB, the mixing of 0.5-3.0% after adding mixing
Weight percentage is the n-butanol of 0.1-1.0%, and 5-10 is stood after being stirred 5-15 minutes with 500-900 revs/min of rotating speed
Minute, the tetraethyl orthosilicate of amount 0.5-5% of cabaltous nitrate hexahydrate material is added thereafter simultaneously with 120-200 revs/min
Rotating speed stands 3-10 hours after stirring 2-5 minutes；By the solution 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；The titanate coupling agent of the solid and solid masses percentage 0.2-0.8% for obtaining will be collected, consolidated
The Zinc diacetate dihydrate of weight percentage 0.5-5%, the glycerine of solid masses percentage 0.2-1% and hexamethylene are with volume
Than being put into ball mill after the mixing liquid mixing for 1: 1, ball milling is 20: 1 with the mass ratio of material, with 200-400 revs/min
Speed ball milling 10-20 hours, ball milling takes out material after finishing, and is put into after drying 10-20 hours in 60 DEG C of -80 DEG C of drying boxes
In tube furnace, air to gas pressure is less than 0.5-3Pa in extracting tube furnace, and 75-95 is warmed up to 2-10 DEG C/min of speed
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-1
Purity higher than percent by volume 99.9% argon gas, and simultaneously with 20-30 DEG C/min of speed be warmed up to 120-130 DEG C and
Kept for 5-15 minutes at a temperature of this；Double-component cladding Ni is obtained2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material.
2. double-component according to claim 1 coats Ni2+、Cu2+The preparation side of doping amorphous cobalt nitrate lithium cell negative pole material
Method, it is characterised in that above-mentioned titanate coupling agent is isopropyl three (dioctyl pyrophosphate) titanate esters, two (dioctyl pyrophosphoryls
Base) close one kind in fluoroacetic acid ester titanium, tetra isopropyl two (phosphorous acid dilauryl) titanate esters.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993134A (en) * | 2015-06-08 | 2015-10-21 | 宁波大学 | Preparation method of lithium ion battery copper nitrate composite negative electrode material |
| CN104993147A (en) * | 2015-06-08 | 2015-10-21 | 宁波大学 | Method for preparing multilevel structure copper nitrate anode material |
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2017
- 2017-01-17 CN CN201710057524.8A patent/CN106848304A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993134A (en) * | 2015-06-08 | 2015-10-21 | 宁波大学 | Preparation method of lithium ion battery copper nitrate composite negative electrode material |
| CN104993147A (en) * | 2015-06-08 | 2015-10-21 | 宁波大学 | Method for preparing multilevel structure copper nitrate anode material |
Non-Patent Citations (1)
| Title |
|---|
| XI ZHENG 等: "Improved electrochemical property ofcopper nitrate hydrate by multiwall carbon nanotube", 《ELECTROCHIMICA ACTA》 * |
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Application publication date: 20170613 |