CN105914368A - Preparation method of silicate composite positive electrode material - Google Patents
Preparation method of silicate composite positive electrode material Download PDFInfo
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- CN105914368A CN105914368A CN201610303920.XA CN201610303920A CN105914368A CN 105914368 A CN105914368 A CN 105914368A CN 201610303920 A CN201610303920 A CN 201610303920A CN 105914368 A CN105914368 A CN 105914368A
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- composite positive
- silicate composite
- positive pole
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- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method of a silicate composite positive electrode material. According to the preparation method, firstly, a conducting agent is soaked in concentrated nitric acid; the stirring is performed at 80 to 150 DEG C; the treated conducting agent is obtained; the treated conducting agent is dispersed into an organic solvent to obtain a dispersing solution; then, the dispersing solution is heated to 120 to 180 DEG C; then, a water solution containing an iron source is added for reaction to obtain a precursor; the obtained precursor, lithium sources and silicon sources are added into water and are mixed; then an organic acid complexing agent is added; stirring is carried out until the gel is formed; the obtained gel is dried and ground; then, sintering is performed under the gas protection condition at 500 to 900 DEG C; cooling and grinding are performed to obtain the silicate composite positive electrode material. The silicate composite positive electrode material provided by the invention has the advantages that the three-dimensional porous structures is used; good conducting capability is realized; the charging and discharging volume and good magnification performance are realized; the silicate composite positive electrode material belongs to a high-performance lithium ion battery positive electrode material with potentials.
Description
Technical field
The present invention relates to lithium ion battery material technical field, particularly relate to a kind of silicate composite positive pole
Preparation method.
Background technology
Along with development and the continuous progress of human civilization of society, the demand of portable energy source is drastically increased by people
Long, more and more higher to its performance requirement.Additionally, electric automobile drives becoming 21st century potential gasoline
The replacer of electrical automobile and receive much attention, and portable power source system is the key of restriction electric automobile industry development
Technology.But the positive electrode actual specific capacity of major part portable power source is on the low side at present, is just improving lithium ion battery
The capacity of pole is the key problem of research.
Since two thousand five, with ferric metasilicate lithium (Li2FeSiO4) and manganese silicate of lithium (Li2MnSiO4) it is generation
The silicate anodal of table receives much concern due to its higher energy density.These silicate materials in theory may be used
With two lithium ions of deintercalation, specific capacity is up to 330mAh.g-1, it is 2 times of current commercialization positive electrode.
And, they also have ABUNDANT NATUREAL RESOURSES, with low cost, environmental friendliness, are readily synthesized and high security
Etc. advantage.Due to Li2MnSiO4Structure gradually amorphization in cyclic process and to lose major part electrochemistry special
Levy, therefore, Li2FeSiO4It it is the material having most application prospect in silicate anodal.
But Li2FeSiO4Electronic conductivity extremely low, the solid-state diffusion of lithium ion is the slowest, therefore material charge and discharge
Dynamic polarization in electric process is serious, it is difficult to obtain actual high power capacity.In order to improve Li2FeSiO4Material
Actual capacity, researchers devise multiple modified scheme.These schemes mainly include reduce scantling,
Ion doping and material with carbon element are combined.The Chinese patent of Application No. 201510061167.3 discloses preparation
The method of nanoporous silicic acid iron lithium, nano material can shorten lithium ion transport distance, thus improve electrode
Reaction speed；The Chinese patent of Application No. 201210207841.0 discloses vanadium doping and improves ferric metasilicate lithium electricity
The method of electronic conduction ability；The Chinese patent of Application No. 201410136971.9 discloses graphene coated silicon
The method of acid iron lithium；Guan et al. there was reported one and passes through SiO2Middle of the road prepares Li2FeSiO4With carbon
The way (J.Mater.Chem.2012,22,18797) of nanotube (CNT) composite construction.Graphene and
The compound electronic conduction ability that can be effectively improved material system of CNT, thus improve Li2FeSiO4
Charge/discharge capacity, but the improvement to the ion conductivity of material is the most limited.Therefore, development low cost,
High power capacity, environment amenable lithium ion battery become the problem that portable power source industry needs solution badly.
In view of drawbacks described above, the design people's the most in addition research and innovation, compound just to founding a kind of silicate
The preparation method of pole material so that it is have more the value in industry.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide the system of a kind of silicate composite positive pole
Preparation Method, the three-dimensional porous structure of this silicate composite positive pole, improve conductive capability and the lithium of material
The transmission performance of ion so that this silicate composite positive pole has higher charge/discharge capacity and good
High rate performance.
The preparation method of a kind of silicate composite positive pole of the present invention, comprises the following steps:
(1) conductive agent is immersed in red fuming nitric acid (RFNA), stirs at 80-150 DEG C, obtain the conductive agent processed；
(2) conductive agent that step (1) processed is distributed in organic solvent obtain dispersion liquid, then will divide
Scattered liquid is heated to 120-180 DEG C, is subsequently adding the aqueous solution of ferric source and reacts, obtaining presoma；
(3) presoma, lithium source and silicon source that step (2) obtains are added to the water and mix, the most again
Adding organic acid complexing agent, stirring is until forming gel；
(4) gel drying that step (3) obtained, grinding, then at 500-900 DEG C under gas shield
Lower sintering, cool down, grind after obtain silicate composite positive pole.
Further, conductive agent is CNT, and conductive agent accounts for the mass fraction of silicate composite positive pole
For 2-30%.
Further, in step (2), source of iron is that ferric nitrate, ferrous acetate, ironic citrate and oxalic acid are sub-
One or more in iron.
Further, in step (2), organic solvent is ethylene glycol, diethylene glycol, glycerine or N, N '-
One in dimethylformamide.
Further, in step (3), lithium source be the one in lithium carbonate, lithium acetate and lithium hydroxide or
Several.
Further, in step (3), silicon source is in silica, tetraethyl orthosilicate and lithium metasilicate
One or more.
Further, in step (3), organic acid complexing agent is ascorbic acid, acetic acid, tartaric acid, lemon
One or more in lemon acid and polyacrylic acid.
Further, in step (3), stir at 50-80 DEG C.
Further, in step (4), gas is one or more in nitrogen, carbon dioxide and argon gas.
Further, in silicate composite positive pole, the mol ratio of iron, lithium and silicon is 0.95-1.05:1.9-2.2:
0.95-1.05。
By such scheme, the invention have the advantages that this silicate composite positive pole comprises internal layer and is
CNT core, outer layer are Li2FeSiO4Coaxial construction；By introducing CNT in material structure, build
Three-dimensional cross-linked loose structure, shortens the diffusion path of lithium ion, improves ion conduction rate；CNT is coaxial
Structure is that electric transmission provides fast path, improves electron transfer rate, accelerates the discharge and recharge of material
Dynamic process；The inventive method is simple to operate, and sintering time is short, and energy loss is few, with low cost, institute
The silicate composite positive pole of preparation has higher charge/discharge capacity and good high rate performance, has good
Good application prospect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technology of the present invention
Means, and can being practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate attached
After figure describes in detail such as.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the ferric metasilicate lithium composite positive pole of the embodiment of the present invention 1 preparation；
Fig. 2 is the scanning electron microscope diagram of the ferric metasilicate lithium composite positive pole of the embodiment of the present invention 1 preparation；
Fig. 3 is the charging and discharging curve figure of the ferric metasilicate lithium composite positive pole of the embodiment of the present invention 1 preparation；
Fig. 4 is the charging and discharging curve figure of the ferric metasilicate lithium composite positive pole of the embodiment of the present invention 2 preparation.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the detailed description of the invention of the present invention is described in further detail.With
Lower embodiment is used for illustrating the present invention, but is not limited to the scope of the present invention.
Embodiment 1
Take 2g CNT (CNT) to be immersed in red fuming nitric acid (RFNA), stir 5 hours at 80 DEG C；Take 0.5g
The CNT that red fuming nitric acid (RFNA) processed is dispersed in ethylene glycol, is warming up to 170 DEG C, adds vinegar while stirring
The ferrous aqueous solution of acid, and continue to stir 1 hour, obtain the coaxial presoma of CNT and FeOOH；Will
Above-mentioned coaxial presoma and lithium acetate, silica are that 1:2.2:1 is at deionization by the mol ratio of Fe:Li:Si
Mixing in water, be subsequently adding tartaric acid, tartaric acid is 2:1 with the mol ratio of Fe, stirs 3 little at 80 DEG C
Time formed colloidal sol；Continue stirring 9 hours, form gel；By gel drying, grinding, then protect at argon gas
Protect down in 650 DEG C be calcined 24 hours, cool down, grind after obtain ferrosilicon silicate of lithium composite positive pole.Such as figure
Shown in 1 and Fig. 2, the X-ray diffraction pattern of this material meets orthorhombic crystal phase, and pattern is three-dimensional porous structure.
Charge-discharge test shows, the discharge capacity of this composite reaches 221mAh.g-1, as shown in Figure 3.
Embodiment 2
Take 2g CNT (CNT) to be dipped in red fuming nitric acid (RFNA), stir 2 hours at 150 DEG C；Take 0.2g
The CNT that red fuming nitric acid (RFNA) processed is dispersed in glycerine, is warming up to 130 DEG C, adds nitric acid while stirring
Water solution, and continue to stir 3 hours, obtain the coaxial presoma of CNT and FeOOH；By above-mentioned
Coaxial presoma and lithium acetate, tetraethyl orthosilicate are that 1:2.05:1 is in deionized water by the mol ratio of Fe:Li:Si
Middle mixing, is subsequently adding ascorbic acid, and ascorbic acid and Fe mol ratio are 1:1, stirs 3.5 at 70 DEG C
Hour formed colloidal sol；Continue stirring 10 hours, form gel；By gel drying, grinding, then at argon gas
Under be calcined 12 hours in 700 DEG C, then cool down, grind, obtain ferrosilicon silicate of lithium composite positive pole.Such as figure
Shown in 4, the discharge capacity of this silicate composite positive pole reaches 193mAh.g-1。
Embodiment 3
Take 2g CNT (CNT) to be dipped in red fuming nitric acid (RFNA), stir 3 hours at 100 DEG C；Take 0.2g
The CNT that red fuming nitric acid (RFNA) processed is dispersed in N, in N '-dimethyl formamide, is warming up to 120 DEG C, while stir
Mix limit and add the ironic citrate aqueous solution, and continue to stir 2 hours, obtain CNT coaxial with FeOOH
Presoma；By above-mentioned coaxial presoma with lithium hydroxide, tetraethyl orthosilicate by the mol ratio of Fe:Li:Si it is
1:2.1:0.95 mixes in deionized water, is subsequently adding citric acid, and citric acid is 2:1 with the mol ratio of Fe,
Stir at 50 DEG C 8 hours and form colloidal sol；Continue stirring and obtain gel in 24 hours；By gel drying, grinding,
Then it is calcined 3 hours in 800 DEG C under argon hydrogen mixture, then cools down, grind, obtain ferrosilicon silicate of lithium multiple
Close positive electrode.The discharge capacity of this silicate composite positive pole reaches 182mAh.g-1。
Embodiment 4
Take 1.5g CNT (CNT) in red fuming nitric acid (RFNA) 120 DEG C stir 4 hours；Take at 0.3g red fuming nitric acid (RFNA)
The CNT managed is dispersed in diethylene glycol, is warming up to 180 DEG C, adds ferrous oxalate while stirring
Acidic aqueous solution, and continue to stir 4 hours, obtain the coaxial presoma of CNT and FeOOH；By upper
Stating coaxial presoma with lithium metasilicate is that 0.95:2:1.05 mixes, so in deionized water by the mol ratio of Fe:Li:Si
Rear addition acetic acid, forms gel in continuously stirred 24 hours at 80 DEG C；By the gel drying obtained, grinding,
It is calcined 0.5 hour in 900 DEG C the most under a nitrogen, then cools down, grind, obtain ferrosilicon silicate of lithium anode composite
Material.The discharge capacity of this silicate composite positive pole is 177mAh.g-1。
Embodiment 5
1.5g CNT is stirred 5 hours at 120 DEG C in red fuming nitric acid (RFNA)；Take the CNT that 0.3g red fuming nitric acid (RFNA) processed
It is dispersed in ethylene glycol, is warming up to 160 DEG C, adds the aqueous solution of ferrous acetate while stirring, and continue
Stir 5 hours, obtain the coaxial presoma of CNT and FeOOH；By above-mentioned coaxial presoma and acetic acid
Lithium, silica are mixed, then in deionized water in the ratio that the mol ratio of Fe:Li:Si is 1.05:2:1.05
Add ascorbic acid, stir at 60 DEG C 10 hours and form colloidal sol, continue stirring 10 hours, form gel；
By gel drying, grinding, it is calcined 6 hours in 750 DEG C the most under argon gas, then cools down, grind, obtain silicon
Ferrous silicate lithium composite positive pole.The discharge capacity of this silicate composite positive pole reaches 202mAh.g-1。
This silicate composite positive pole comprises ferric metasilicate lithium active material and carbon nanotube conducting agent, wherein silicon
Acid iron lithium is wrapped in the surface of CNT equably and forms coaxial material, and forms the three-dimensional of porous further
Cross-linked network；Owing to having three-dimensional porous structure and good conductive capability, this silicate anode composite
There is higher charge/discharge capacity and good high rate performance, use ferric metasilicate lithium prepared by the method for the present invention
Composite positive pole, has up to 221mAh.g-1Discharge capacity.
The above is only the preferred embodiment of the present invention, is not limited to the present invention, it is noted that
For those skilled in the art, on the premise of without departing from the technology of the present invention principle, also
Can make some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a silicate composite positive pole, it is characterised in that comprise the following steps:
(1) conductive agent is immersed in red fuming nitric acid (RFNA), stirs at 80-150 DEG C, obtain the conductive agent processed；
(2) conductive agent that step (1) processed is distributed in organic solvent obtain dispersion liquid, then by institute
State dispersion liquid and be heated to 120-180 DEG C, be subsequently adding the aqueous solution of ferric source and react, obtaining presoma；
(3) presoma, lithium source and silicon source that step (2) obtains are added to the water and mix, the most again
Adding organic acid complexing agent, stirring is until forming gel；
(4) gel drying that step (3) obtained, grinding, then at 500-900 DEG C under gas shield
Lower sintering, cool down, grind after obtain described silicate composite positive pole.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
Described conductive agent is CNT, and described in described silicate composite positive pole, the mass fraction of conductive agent is
2-30%.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (2), described source of iron is the one in ferric nitrate, ferrous acetate, ironic citrate and ferrous oxalate
Or it is several.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (2), described organic solvent is ethylene glycol, diethylene glycol, glycerine and N, N '-dimethyl first
One or more in acid amides.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (3), described lithium source is one or more in lithium carbonate, lithium acetate and lithium hydroxide.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (3), described silicon source is one or more in silica, tetraethyl orthosilicate and lithium metasilicate.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (3), described organic acid complexing agent is ascorbic acid, acetic acid, tartaric acid, citric acid and poly-third
One or more in olefin(e) acid.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (3), stir at 50-80 DEG C.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In step (4), described gas is one or more in nitrogen, carbon dioxide and argon gas.
The preparation method of silicate composite positive pole the most according to claim 1, it is characterised in that:
In described silicate composite positive pole, the mol ratio of iron, lithium and silicon is 0.95-1.05:1.9-2.2:0.95-1.05.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101546828A (en) * | 2008-12-27 | 2009-09-30 | 深圳市德方纳米科技有限公司 | Nanometer ferrous silicate lithium material and preparation method thereof |
| JP2013178885A (en) * | 2012-02-28 | 2013-09-09 | Toyota Industries Corp | Positive electrode active material, production method of positive electrode active material, nonaqueous electrolyte secondary battery and vehicle mounting the same |
| CN103746116A (en) * | 2014-01-10 | 2014-04-23 | 国家纳米科学中心 | Carbon-coated ferrous lithium silicate anode material, as well as preparation method and application thereof |
| JP2014120365A (en) * | 2012-12-18 | 2014-06-30 | Taiheiyo Cement Corp | Process of manufacturing positive electrode active material for lithium ion battery |
| CN103985867A (en) * | 2014-05-19 | 2014-08-13 | 电子科技大学 | Method for preparing carbon-coated lithium iron silicate composite material |
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- 2016-05-10 CN CN201610303920.XA patent/CN105914368B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546828A (en) * | 2008-12-27 | 2009-09-30 | 深圳市德方纳米科技有限公司 | Nanometer ferrous silicate lithium material and preparation method thereof |
| JP2013178885A (en) * | 2012-02-28 | 2013-09-09 | Toyota Industries Corp | Positive electrode active material, production method of positive electrode active material, nonaqueous electrolyte secondary battery and vehicle mounting the same |
| JP2014120365A (en) * | 2012-12-18 | 2014-06-30 | Taiheiyo Cement Corp | Process of manufacturing positive electrode active material for lithium ion battery |
| CN103746116A (en) * | 2014-01-10 | 2014-04-23 | 国家纳米科学中心 | Carbon-coated ferrous lithium silicate anode material, as well as preparation method and application thereof |
| CN103985867A (en) * | 2014-05-19 | 2014-08-13 | 电子科技大学 | Method for preparing carbon-coated lithium iron silicate composite material |
Non-Patent Citations (1)
| Title |
|---|
| QINGTANG ZHANG ET AL.: "Nano/micro lithium transitionmetal (Fe,Mn,Co and Ni) silicate cathode materials for lithium ion batteries", 《NANOTECHNOLOGY》 * |
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