CN106784733A - A kind of ZnO coats Ni2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material and preparation method thereof - Google Patents
A kind of ZnO coats Ni2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material and preparation method thereof Download PDFInfo
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Abstract
A kind of ZnO coats Ni2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material and preparation method thereof, it is characterised in that Ni is synthesized using spray drying process2+、Co2+After doping amorphous copper nitrate, using the hydroxyl in the basic salt that particle surface in spray-drying process is formed, using coupling agent Surface coating ZnO, the electronic conduction ability of material is improved；Then in high vacuum conditions, using the crystallization water in specific heat treatment step removal system, ZnO claddings Ni is formed2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material.Doping Ni in system2+、Co2+Ion causes that Cu 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 copper 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 copper 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.Copper 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, copper 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, copper nitrate surface is unstable, is easily corroded by electrolyte.
Therefore it is that nitric acid copper product is made to develop a kind of modified anhydrous nitric acid copper 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 ZnO claddings Ni for existing background technology2+、Co2+Doping amorphous copper nitrate lithium cell negative pole
Material and preparation method, the method synthesize Ni using spray drying process2+、Co2+It is dry using spraying after doping amorphous copper nitrate
Hydroxyl in the basic salt that particle surface is formed during dry, using coupling agent Surface coating ZnO, improves the electronic conduction of material
Ability；Then in high vacuum conditions, using the crystallization water in specific heat treatment step removal system, ZnO claddings Ni is formed2 +、Co2+Doping amorphous copper nitrate lithium cell negative pole material.Doping Ni in system2+、Co2+Ion causes that Cu-O space structures are produced
Distortion, extends lithium ion diffusive migration passage, improves its lithium ion conductivity；It will be particularly beneficial that material is for noncrystal, respectively to
The same sex, is conducive to the quick conduction of lithium ion.So as to increase substantially the comprehensive electrochemical of copper nitrate.
This ZnO coats Ni2+、Co2+Adulterate amorphous copper nitrate lithium cell negative pole material, and its preparation method is：Nitre is hydrated by three
Sour copper, the Nickelous nitrate hexahydrate of the amount 0.5-5% of Gerhardite material, the amount 0.5-5% of Gerhardite material
Cabaltous nitrate hexahydrate dissolving forms total concentration of metal ions for 0.5-1.5molL in deionized water-1Solution, by the solution
With 1-10mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operating conditions are：Intake
0.5-3.5m3·min-1, 100 DEG C -130 DEG C of intake air temperature, 80 DEG C -95 DEG C of air outlet temperature；To collect the solid that obtains with
It is the titanate coupling agent of solid masses percentage 0.2-0.8%, the Zinc diacetate dihydrate of solid masses percentage 0.5-5%, solid
The glycerine and hexamethylene of weight percentage 0.2-1% are put into ball mill, ball after mixing as 1: 1 mixing liquid with volume ratio
The mass ratio of mill and material is 20: 1, and with 200-400 revs/min of speed ball milling 10-20 hours, ball milling finishes rear extract
Material, in being put into tube furnace after drying 10-20 hour in 60 DEG C of -80 DEG C of drying boxes, air is to gas pressure in extraction tube furnace
Less than 0.5-3Pa, it is warmed up to 75-95 DEG C with 2-10 DEG C/min of speed and is kept for 8-15 minutes at this temperature and protected all the time
Pressure is held 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
120-130 DEG C is warmed up to 20-30 DEG C/min of speed and kept for 5-15 minutes at this temperature simultaneously；ZnO claddings are obtained
Ni2+、Co2+Doping amorphous copper 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：Ni is synthesized using spray drying process2+、Co2+Doping amorphous
After copper nitrate, using the hydroxyl in the basic salt that particle surface in spray-drying process is formed, using coupling agent Surface coating
ZnO, improves the electronic conduction ability of material；Then in high vacuum conditions, using in specific heat treatment step removal system
The crystallization water, and cause surface ZnO clads be loose structure；Doping Ni in system2+、Co2+Ion causes that Cu-O is empty
Between structure produce distortion, extend lithium ion diffusive migration passage and improve its lithium ion conductivity.So as to increase substantially nitric acid
The comprehensive electrochemical of copper.
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 Gerhardite, the cabaltous nitrate hexahydrate of the amount 0.6% of Gerhardite material, three hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 0.7% of nitric acid copper material forms total concentration of metal ions for 0.5mol in deionized water
L-1Solution, by the solution with 2mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 0.6m3·min-1, 100 DEG C of intake air temperature, 80 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 0.3%, two hydration vinegar of solid masses percentage 0.5%
Sour zinc, the glycerine of solid masses percentage 0.2% 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 250 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 2Lmin-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 6 minutes at this temperature；ZnO claddings Ni is obtained2+、Co2+Doping amorphous copper nitrate lithium cell negative pole
Material.
Embodiment 2：By Gerhardite, the Nickelous nitrate hexahydrate of the amount 4.5% of Gerhardite material, three hydrations
The cabaltous nitrate hexahydrate dissolving of the amount 4.9% of nitric acid copper material forms total concentration of metal ions for 1.4mol in deionized water
L-1Solution, by the solution with 8mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 3.3m3·min-1, 128 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 in extracting tube furnace
2.5Pa, is warmed up to 95 DEG C and is kept for 15 minutes at this temperature and remain that pressure is less than with 10 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 30 DEG C/min
Speed be warmed up to 130 DEG C and at this temperature keep 15 minutes；ZnO claddings Ni is obtained2+、Co2+Doping amorphous copper nitrate lithium
Cell negative pole material.
Embodiment 3：By Gerhardite, the cabaltous nitrate hexahydrate of the amount 2.5% of Gerhardite material, three hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 3% of nitric acid copper material forms total concentration of metal ions for 1.0molL in deionized water-1
Solution, by the solution with 4mLmin-1Speed the injection port of spray dryer, other operating conditions are passed through by peristaltic pump
For：Intake 3.0m3·min-1, 120 DEG C of intake air temperature, 85 DEG C of air outlet temperature；The solid and solid matter for obtaining will be collected
Measure tetra isopropyl two (phosphorous acid dilauryl) titanate esters, the two hydration vinegar of solid masses percentage 2.5% of percentage 0.4%
Sour 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 2Pa in extracting tube furnace,
85 DEG C are warmed up to 5 DEG C/min of speed and kept for 10 minutes at this temperature and remain that pressure is less than 2Pa；Thereafter lead to
Inbound traffics are 5Lmin-1Purity and is warmed up to 25 DEG C/min of speed simultaneously higher than the argon gas of percent by volume 99.9%
125 DEG C and at this temperature keep 10 minutes；ZnO claddings Ni is obtained2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material.
Embodiment 4：By Gerhardite, the cabaltous nitrate hexahydrate of the amount 0.7% of Gerhardite material, three hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 0.9% of nitric acid copper material forms total concentration of metal ions for 1.3mol in deionized water
L-1Solution, by the solution with 8mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 3.0m3·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
Tetra isopropyl two (phosphorous acid dilauryl) titanate esters of weight percentage 0.6%, two water of solid masses percentage 0.9%
It is put into after zinc acetate, the glycerine of solid masses percentage 0.8% and hexamethylene are closed with volume ratio as 1: 1 mixing liquid mixing
Ball mill, ball milling is 20: 1 with the mass ratio of material, and with 220 revs/min of speed ball milling 13 hours, ball milling takes out after finishing
Material, in being put into tube furnace after being dried 15 hours in 65 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 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 3Lmin-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；ZnO claddings Ni is obtained2+、Co2+Doping amorphous copper nitrate lithium
Cell negative pole material.
Embodiment 5：By Gerhardite, the cabaltous nitrate hexahydrate of the amount 1.4% of Gerhardite material, three hydrations
The Nickelous nitrate hexahydrate dissolving of the amount 1.2% of nitric acid copper material forms total concentration of metal ions for 0.8mol in deionized water
L-1Solution, by the solution with 2mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operations
Condition is：Intake 2.7m3·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
Tetra isopropyl two (phosphorous acid dilauryl) titanate esters of weight percentage 0.6%, two water of solid masses percentage 0.8%
It is put into after zinc acetate, the glycerine of solid masses percentage 0.6% and hexamethylene are closed with volume ratio as 1: 1 mixing liquid mixing
Ball mill, ball milling is 20: 1 with the mass ratio of material, and with 350 revs/min of speed ball milling 15 hours, ball milling takes out after finishing
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
2Pa, is warmed up to 75 DEG C and is kept for 10 minutes at this temperature and remain that pressure is less than 2Pa with 2 DEG C/min of speed；Its
After be passed through flow for 3Lmin-1Purity is higher than the argon gas of percent by volume 99.9%, and simultaneously with 20 DEG C/min of speed liter
Temperature is to 120 DEG C and is kept for 8 minutes at this temperature；ZnO claddings Ni is obtained2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material
Material.
Claims (2)
1. a kind of ZnO coats Ni2+、Co2+The preparation method of doping amorphous copper nitrate lithium cell negative pole material, it is characterized by：By three water
Close copper nitrate, the Nickelous nitrate hexahydrate of the amount 0.5-5% of Gerhardite material, the amount 0.5- of Gerhardite material
5% cabaltous nitrate hexahydrate dissolving forms total concentration of metal ions for 0.5-1.5molL in deionized water-1Solution, will
The solution is with 1-10mLmin-1Speed the injection port of spray dryer is passed through by peristaltic pump, other operating conditions are：Enter
Air quantity 0.5-3.5m3·min-1, 100 DEG C -130 DEG C of intake air temperature, 80 DEG C -95 DEG C of air outlet temperature；By consolidating that collection is obtained
Body and the titanate coupling agent of solid masses percentage 0.2-0.8%, the two hydration acetic acid of solid masses percentage 0.5-5%
Zinc, the glycerine of solid masses percentage 0.2-1% 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, with 200-400 revs/min of speed ball milling 10-20 hours, after ball milling is finished
Material is taken out, in being put into tube furnace after drying 10-20 hour in 60 DEG C of -80 DEG C of drying boxes, air is to gas in extraction tube furnace
Body pressure is less than 0.5-3Pa, is warmed up to 75-95 DEG C with 2-10 DEG C/min of speed and keeps 8-15 minutes at this temperature simultaneously
Remain that pressure is less than 0.5-3Pa；Thereafter flow is passed through for 1-10Lmin-1Argon of the purity higher than percent by volume 99.9%
Gas, and simultaneously with 20-30 DEG C/min of speed be warmed up to 120-130 DEG C and at this temperature keep 5-15 minutes；Being obtained should
ZnO coats Ni2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material.
2. ZnO according to claim 1 coats Ni2+、Co2+The preparation method of doping amorphous copper nitrate lithium cell negative pole material,
It is characterized in that above-mentioned titanate coupling agent is isopropyl three (dioctyl pyrophosphate) titanate esters, two (dioctyl pyrophosphoryl bases)
Close the 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 |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-01-17 CN CN201710062461.5A patent/CN106784733A/en active Pending
Patent Citations (2)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| XI ZHENG等: "Improved electrochemical property of copper nitrate hydrate by multiwall carbon nanotube", 《ELECTROCHIMICA ACTA》 * |
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Application publication date: 20170531 |