CN104900853B - A kind of synthesis in solid state Co2+Doping fluorination bismuth anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of synthesis in solid state Co2+Doping fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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Abstract
A kind of synthesis in solid state Co2+Doping fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, this method uses the quaternary ammonium salt using fluorine as anion to be raw material, the space steric effect by the macoradical and effect solid phase by specific adjuvant directly synthesizes fluorination bismuth, while passing through Co2+Doping improves the electronic conductivity of material, and the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries‑1Specific capacity.This method equipment requirement is low, and product purity is high, is avoided that in solid phase reaction generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high power capacity fluorination bismuth complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with
Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass
The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity
Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic
Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided
Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode
Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment
The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time
Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present
The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and
Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years
Come, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, screening
Up to tens of kinds of the lithium ion cell positive gone out, but really have potential commercial applications prospect or be already present in the market just
Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance
It is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material capacity
Circulate holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long
Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively
275mAh/g and 285mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And
Progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity
About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature
Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium
Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and
And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and
The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode
The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation
Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell
Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine
The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole
All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and
Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole
In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F,
Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10)：
A1318-A1327.]：
nLi++MeFn+ne-→nLiF+Me0
It can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel
The attention of degree.Wherein fluorination bismuth is due to there is about 7170WhL-1Volume and capacity ratio and have big advantage.Conventional fluorine
Change the synthetic method of bismuth to be carried out with metal simple-substance with metal oxide/hydroxide or fluorine gas with hydrogen fluoride gas at high temperature
Reaction, process conditions are harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares fluorination bismuth
Then it can not often be used because by-products content is too high as positive electrode while also lacking warp because producing many costs height of waste liquid
Ji property.Bismuth, which is fluorinated, as lithium ion secondary battery anode material also has a negative characteristic to be that its electronic conductivity is extremely low,
Therefore very high polarizing voltage can be caused in charge and discharge process.Ion doping is a kind of microcosmic knot of effective regulation lattice
Structure, changes the means of lattice electron and ionic transport properties, it is possible to improve the chemical property of material.However, ion doping
Even polyion collaboration doping is extremely complex to the mechanism of action of parent, and effect is often difficult to expect.
Therefore a kind of simple technique, product quality stabilization are developed, bismuth system is fluorinated with excellent electrochemical performance synthesis in solid state
Preparation Method is to be fluorinated the key that bismuth material is applied as secondary cell.
The content of the invention
The present invention proposes a kind of synthesis in solid state Co for existing background technology2+Doping fluorination bismuth lithium ion cell positive material
Material and preparation method thereof, this method uses the quaternary ammonium salt using fluorine as anion to be raw material, passes through the space steric effect of macoradical
And fluorination bismuth is directly synthesized by the effect solid phase of specific adjuvant, while passing through Co2+Doping improves the electronic conductivity of material,
The fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries-1Specific capacity.This method equipment will
Ask low, product purity is high, be avoided that in solid phase reaction generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent
Chemical property.
This synthesis in solid state Co2+Doping fluorination bismuth method for preparing anode material of lithium-ion battery, it is characterized in that：By bismuth salt,
Ball mill, ball milling and thing are put into after the auxiliary agent Z1 mixing of the amount 0.5-2% of bismuth salt material cobalt salt and bismuth salt quality 0.5-2%
The mass ratio of material is 20: 1, and with 200-400 revs/min of speed ball milling 10-20 hours, this material is referred to as into material I；Will be with fluorine
The 0.5-2% of quaternary ammonium salt quality for the quaternary ammonium salt of anion, by anion of fluorine auxiliary agent Z2, using fluorine as the quaternary ammonium of anion
Ball mill is put into after the 2-4% of salt quality absolute ethyl alcohol mixing, the mass ratio of ball milling and material is 20: 1, with 200-400
Rev/min speed ball milling 10-20 hours, this material is referred to as material II；Material I, material II are put into ball mill, ball milling
Mass ratio with material is 20: 1, while it is 95: 5 nitrogen for atmospheric pressure and mixing for ammonia that volume ratio is filled with ball grinder
Gas is closed, with 300-400 revs/min of speed ball milling 5-10 hours；Material after ball milling is taken out, after three times are washed, 100
This obtained Co after being dried 10-20 hour in DEG C -120 DEG C of drying boxes2+Doping fluorination bismuth.
Bismuth salt in preparation method as described above is one kind in five nitric hydrate bismuths, bismuth chloride；Cobalt salt is six hydrations
One kind in cobalt nitrate, Cobaltous oxalate,tetrahydrate, cobalt chloride hexahydrate；Auxiliary agent Z1 is perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, complete
One kind in fluorine glutaric acid；Auxiliary agent Z2 is one kind in Tween-60, op-10, Arlacel-80；Quaternary ammonium salt using fluorine as anion is
One kind in tetra-n-butyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride；In material I the amount of the material of bismuth salt with
The ratio of the amount of quaternary ammonium material is 1: 3 in material II.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of the material, voltage range
1.8V-4.0V, charging and discharging currents 0.1C.
Compared with prior art, the advantage of the invention is that：It is raw material to use the quaternary ammonium salt using fluorine as anion, by big
The space steric effect of group simultaneously directly synthesizes fluorination bismuth by the effect solid phase of specific adjuvant, while passing through Co2+Doping is improved
The electronic conductivity of material, the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries-1Ratio
Capacity.This method equipment requirement is low, and product purity is high, is avoided that in solid phase reaction a variety of double salt of generation fluorination bismuth etc. are secondary anti-
Answer product and with excellent chemical property.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V-
4.0V, charging and discharging currents 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By five nitric hydrate bismuths, the cabaltous nitrate hexahydrate and five water of the amount 0.5% of five nitric hydrate bismuth materials
Ball mill is put into after the perfluoro-heptanoic acid mixing for closing bismuth nitrate quality 0.5%, the mass ratio of ball milling and material is 20: 1, with 200
Rev/min speed ball milling 10 hours, this material is referred to as material I；By tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium fluoride quality
0.5% Tween-60, be put into ball mill after the 2% absolute ethyl alcohol mixing of tetra-n-butyl ammonium fluoride quality, ball milling and thing
The mass ratio of material is 20: 1, and with 200 revs/min of speed ball milling 10 hours, this material is referred to as into material II；By material I and thing
Material II is put into ball milling according to the ratio of the amount of quaternary ammonium material in the amount and material II of the material of bismuth salt in material I for 1: 3 ratio
The mass ratio of machine, ball milling and material is 20: 1, while being filled with nitrogen of the volume ratio for 95: 5 atmospheric pressure in ball grinder
With the mixed gas of ammonia, with 300 revs/min of speed ball milling 5 hours；Material after ball milling is taken out, after three times are washed,
This Co is made after being dried 10 hours in 100 DEG C of drying boxes2+Doping fluorination bismuth.
Embodiment 2：By the 2,2- of bismuth chloride, the Cobaltous oxalate,tetrahydrate of the amount 1% of bismuth chloride material and bismuth chloride quality 1%
Ball mill is put into after the mixing of difluoro cyclopropyl carboxylic acid, the mass ratio of ball milling and material is 20: 1, with 200 revs/min of speed ball
Mill 10 hours, is referred to as material I by this material；By Methanaminium, N,N,N-trimethyl-, fluoride, 1% op-10, the tetramethyl of Methanaminium, N,N,N-trimethyl-, fluoride quality
Be put into ball mill after the 3% absolute ethyl alcohol mixing of ammonium fluoride quality, the mass ratio of ball milling and material is 20: 1, with 300 turns/
The speed ball milling of minute 15 hours, is referred to as material II by this material；By materials of the material I and material II according to bismuth salt in material I
Amount and material II in the ratio of amount of quaternary ammonium material be put into ball mill for 1: 3 ratio, the mass ratio of ball milling and material is
20: 1, while be filled with nitrogen and the mixed gas of ammonia of the volume ratio for 95: 5 atmospheric pressure in ball grinder, with 350 turns/
The speed ball milling of minute 7 hours；Material after ball milling is taken out, after three times are washed, after being dried 15 hours in 110 DEG C of drying boxes
This Co is made2+Doping fluorination bismuth.
Embodiment 3：By the perfluor of bismuth chloride, the cobalt chloride hexahydrate of the amount 2% of bismuth chloride material and bismuth chloride quality 2%
Ball mill is put into after glutaric acid mixing, the sub mass ratio with material of ball milling is 20: 1, small with 400 revs/min of speed ball milling 20
When, this material is referred to as material I；By benzyl trimethyl ammonium fluoride, 2% Arlacel-80, the benzyl of benzyl trimethyl ammonium fluoride quality
Ball mill is put into after the 4% absolute ethyl alcohol mixing of base trimethyl ammonium fluoride quality, the sub mass ratio with material of ball milling is 20: 1,
With 400 revs/min of speed ball milling 20 hours, this material is referred to as material II；By material I and material II according to bismuth in material I
The ratio of the amount of quaternary ammonium material is put into ball mill, ball milling and material for 1: 3 ratio in the amount and material II of the material of salt
Mass ratio is 20: 1, while nitrogen and the mixed gas of ammonia of the volume ratio for 95: 5 atmospheric pressure are filled with ball grinder,
With 400 revs/min of speed ball milling 10 hours；Material after ball milling is taken out, after three times are washed, is done in 120 DEG C of drying boxes
This Co is made after dry 20 hours2+Doping fluorination bismuth.
Embodiment 4：By five nitric hydrate bismuths, the Cobaltous oxalate,tetrahydrate and five water of the amount 1.5% of five nitric hydrate bismuth materials
Ball mill is put into after the perfluoroglutaric acid mixing for closing bismuth nitrate quality 0.7%, the sub mass ratio with material of ball milling is 20: 1, with
350 revs/min of speed ball milling 13 hours, is referred to as material I by this material；By benzyl trimethyl ammonium fluoride, benzyl trimethyl fluorine
Ball milling is put into after changing 1.5% Arlacel-80 of ammonium quality, the 3.5% absolute ethyl alcohol mixing of benzyl trimethyl ammonium fluoride quality
Machine, ball milling is 20: 1 with the mass ratio of material, and with 300 revs/min of speed ball milling 17 hours, this material is referred to as into material
II；According to the ratio of the amount of quaternary ammonium material in the amount of the material of bismuth salt in material I and material II it is 1: 3 by material I and material II
Ratio be put into ball mill, the mass ratio of ball milling and material is 20: 1, while it is 95: 5 one that volume ratio is filled with ball grinder
The nitrogen of individual atmospheric pressure and the mixed gas of ammonia, with 380 revs/min of speed ball milling 8 hours；Take out material after ball milling, warp
Cross after three washings, this Co is made after being dried 15 hours in 115 DEG C of drying boxes2+Doping fluorination bismuth.
Embodiment 5：By five nitric hydrate bismuths, the Cobaltous oxalate,tetrahydrate of the amount 1% of five nitric hydrate bismuth materials and five hydrations
Ball mill is put into after the perfluoroglutaric acid mixing of bismuth nitrate quality 0.5%, the mass ratio of ball milling and material is 20: 1, with 200
Rev/min speed ball milling 20 hours, this material is referred to as material I；By Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride quality
Ball mill, ball milling and material are put into after 1% Arlacel-80, the 3.5% absolute ethyl alcohol mixing of Methanaminium, N,N,N-trimethyl-, fluoride quality
Mass ratio is 20: 1, and with 200 revs/min of speed ball milling 15 hours, this material is referred to as into material II；By material I and material II
According to the ratio of the amount of quaternary ammonium material in the amount and material II of the material of bismuth salt in material I ball mill, ball are put into for 1: 3 ratio
The mass ratio of mill and material is 20: 1, while being filled with nitrogen and ammonia of the volume ratio for 95: 5 atmospheric pressure in ball grinder
Mixed gas, with 350 revs/min of speed ball milling 7 hours；Material after ball milling is taken out, after three times are washed, at 120 DEG C
This Co is made after being dried 19 hours in drying box2+Doping fluorination bismuth.
Claims (2)
1. a kind of synthesis in solid state Co2+Doping fluorination bismuth anode material for lithium-ion batteries preparation method, it is characterised in that by bismuth salt,
Ball mill, ball milling and thing are put into after the auxiliary agent Z1 mixing of the amount 0.5-2% of bismuth salt material cobalt salt and bismuth salt quality 0.5-2%
The mass ratio of material is 20: 1, and with 200-400 revs/min of speed ball milling 10-20 hours, this material is referred to as into material I；Will be with fluorine
The 0.5-2% of quaternary ammonium salt quality for the quaternary ammonium salt of anion, by anion of fluorine auxiliary agent Z2, using fluorine as the quaternary ammonium of anion
Ball mill is put into after the 2-4% of salt quality absolute ethyl alcohol mixing, the mass ratio of ball milling and material is 20: 1, with 200-400
Rev/min speed ball milling 10-20 hours, this material is referred to as material II；Material I, material II are put into ball mill, ball milling
Mass ratio with material is 20: 1, while it is 95: 5 nitrogen for atmospheric pressure and mixing for ammonia that volume ratio is filled with ball grinder
Gas is closed, with 300-400 revs/min of speed ball milling 5-10 hours；Material after ball milling is taken out, after three times are washed, 100
This obtained Co after being dried 10-20 hour in DEG C -120 DEG C of drying boxes2+Doping fluorination bismuth；
Bismuth salt in preparation method as described above is one kind in five nitric hydrate bismuths, bismuth chloride；Cobalt salt is six nitric hydrates
One kind in cobalt, Cobaltous oxalate,tetrahydrate, cobalt chloride hexahydrate；Auxiliary agent Z1 is perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, perfluor penta
One kind in diacid；Auxiliary agent Z2 is one kind in Tween-60, op-10, Arlacel-80；Quaternary ammonium salt using fluorine as anion is four just
One kind in butyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride；The amount of bismuth salt material and material II in material I
The ratio of the amount of middle quaternary ammonium material is 1: 3.
2. synthesis in solid state Co according to claim 12+The preparation method of doping fluorination bismuth anode material for lithium-ion batteries, its
It is characterised by that the fluorination bismuth prepared is used with more than 200mAh.g as anode material for lithium-ion batteries-1Specific capacity.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0558255A1 (en) * | 1992-02-24 | 1993-09-01 | Medtronic, Inc. | Electrochemical cells with end-of-service indicator |
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN101931072A (en) * | 2009-06-26 | 2010-12-29 | 能原材公司 | Anode active material and secondary lithium battery |
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| US9048497B2 (en) * | 2012-10-05 | 2015-06-02 | Rutgers, The State University Of New Jersey | Metal fluoride compositions for self formed batteries |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0558255A1 (en) * | 1992-02-24 | 1993-09-01 | Medtronic, Inc. | Electrochemical cells with end-of-service indicator |
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN101212050A (en) * | 2007-12-21 | 2008-07-02 | 湘潭大学 | Method for producing bismuth trifluoride anode material of Li secondary battery |
| CN101931072A (en) * | 2009-06-26 | 2010-12-29 | 能原材公司 | Anode active material and secondary lithium battery |
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