CN102723465A - Preparation method of porous LiFePO4 bulk electrode for lithium ion batteries - Google Patents
Preparation method of porous LiFePO4 bulk electrode for lithium ion batteries Download PDFInfo
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Abstract
The invention, relating to the field of lithium ion batteries, belongs to a preparation technique of phosphate bulk electrodes and an accurate electrode material characterization technique, particularly discloses a preparation method of a porous LiFePO4 bulk electrode containing no adhesive and no organic solvent for lithium ion batteries. The invention is suitable for improving high capacity bulk electrodes and let the characteristics of electrode material performance be predicted accurately. The method comprises the following steps: mixing a certain amount of cathode materials with organic matter, and carrying out cold pressing into blocks; then acquiring a positive bulk electrode with a porous structure by low temperature sintering, or simultaneously uniformly coating the surface of the porous LiFePO4 particles with a layer of continuous conductive carbon film to obtain excellent conductivity. According to the invention, the problems of long and complex process of conventionally preparing LiFePO4 positive plates, need of various process equipment, and expensive adhesives and solvents for dissolving the adhesives are solved; on that basis, the problem that the use of membrane electrodes predicts the electrochemical performance of the LiFePO4 cathode materials inaccurately in conventional characterization is solved.
Description
Technical field
The present invention relates to the lithium ion battery field, the technology of preparing that belongs to phosphate type block electrode reaches electrode material characterization technique accurately, is specially a kind of lithium ion battery that does not contain any adhesive and organic solvent and uses porous LiFePO
4The preparation method of block electrode is applicable to and improves big capacity block electrode and can accurately characterize the electrode material performance.
Background technology
Along with human living standard's continuous progress, people increase the serious hope that possesses high power capacity small size battery day by day.Lithium battery is the battery of the performance that energy density is the highest in the secondary chemical sources of electric energy used of all commercializations so far, but himself capacity less than normal has still satisfied not the requirement of large scale equipment.Therefore, a large amount of in recent years scientific research energy is used for research and development and possesses high power capacity is arranged (energy) electrode cheaply.But, receive traditional and complicated electrode fabrication and coarse electrochemical Characterization means, make the lithium ion battery overall performance further improve and be restricted.
Lithium ion battery is made up of positive pole, negative pole, barrier film and electrolyte four parts.For traditional electrode preparation technology, positive active material and negative electrode active material are coated on the metal forming as collector, and usually, aluminium foil is as positive collector, and Copper Foil is as negative collector.Shown in Fig. 1 (a), traditional LiFePO
4The preparation flow of positive plate comprises: mix LiFePO
4Positive electrode, conductive agent, adhesive slurrying → coating → roll-in → cutting → drying obtain LiFePO
4Positive plate.This technological process is complicated, needs adhesive and kinds of processes equipment, and the electrode manufacturing cost is high, sees also document Nature 414,359-367, and (2001) are said.
In the laboratory, will stamp out corresponding less thin-film electro pole piece with drift through the prepared membrane electrode that goes out of traditional preparation process technology.The amount of the active material that this pole piece is contained generally is no more than 5mg/cm
2, therefore very harsh to the requirement of electronic balance.Add the required thick insulating polymer glue of preparation electrode slurry, the precise proportioning electrode slurry is brought further difficulty.So, through chemical property that above-mentioned conventional method characterized out and cause bigger error easily.
Summary of the invention
The object of the present invention is to provide a kind of do not use organic bond and metal collector be used to prepare lithium ion battery porous LiFePO
4The method of block electrode.This method has been improved the chemical property of block electrode significantly, has shortened conventional process flow, has solved conventional preparation LiFePO
4The technology of positive plate redundant and complicated needs the problem of the solvent of plurality of devices and expensive adhesive and dissolved adhesive.And the amount of the active material that is contained in the unit volume gets a promotion greatly.Therefore, chemical property that can more accurate exosyndrome material intrinsic.
Technical scheme of the present invention is:
Shown in Fig. 1 (b), the present invention is through evenly mixing LiFePO
4Behind organic substance, the method through cold moudling makes its moulding again.Low-temperature sintering makes LiFePO
4Positive electrode and LiFePO
4The mutual connection of particle forms loose structure simultaneously, or will form the LiFePO of loose structure again
4The method of particle surface through chemical vapour deposition (CVD) evenly coats one deck conductive carbon film and obtains porous, electrically conductive LiFePO
4The block electrode.Its concrete steps are following:
(1) synthesizes electrode material LiFePO
4Powder; Subsequently powder is mixed with the organic substance pore creating material uniformly, organic substance accounts for the 0wt%-90wt% (being preferably 30wt%-60wt%) of mixture gross mass, with the dried powder that mixes cold moudling in mould; The pressure 1-500MPa that colds pressing colds pressing time 1-6000 second.
Synthesize electrode material LiFePO
4The process of powder is a routine techniques, sees also document Nature 414,359-367, (2001).
(2) block of forming is put into the flat-temperature zone of tube furnace; Feed protective gas after discharging furnace air subsequently; Carry out the draining processing in constant temperature 10-60 minute after then being warming up to design temperature 200-400 ℃ and form loose structure; The technical parameter of loose structure: porosity 10%-99% (being preferably 50-90%) has macroporous structure, central hole structure and microcellular structure, and the volume fraction of whole pore volumes that macroporous structure is shared is 1%-99% (being preferably 30-60%); The volume fraction of whole pore volumes that central hole structure is shared is 1%-99% (being preferably 30-60%), and all the other are microcellular structure; Macroporous structure aperture 50nm-500 μ m (the macroporous structure aperture does not contain 50nm), central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.After temperature rises to 500-800 ℃ subsequently, carried out sintering processes in constant temperature 10-180 minute.
Or feed carbon-source gas again and carry out chemical vapour deposition (CVD), forming the LiFePO of loose structure
4Particle surface evenly coats one deck conductive carbon and obtains porous, electrically conductive LiFePO
4The block electrode, the thickness of conductive carbon is: 1-100nm.
The parameter of chemical vapour deposition (CVD) is following:
The carbon-source gas percent by volume is 1-20%, 500-800 ℃ of chemical vapour deposition (CVD) temperature, sedimentation time 10 minutes-3 hours; Post-depositional sample naturally cools to room temperature with stove, takes out to obtain porous, electrically conductive LiFePO
4The block electrode.
Among the present invention, organic substance is a kind of or two or more mixture of citric acid, melamine, saccharomycete, glucose, sucrose, maltose.
Among the present invention, employed LiFePO
4Particle diameter be 10nm-100 μ m.
Among the present invention, said tube furnace is horizontal type stove or shaft (tower) furnace.
Among the present invention, the mode of said discharge furnace air and water vapour is for vacuumizing or use inert gas purge.
Among the present invention, the said carbon-source gas of step (2) is acetylene or propylene.
Among the present invention, said protective gas is one of nitrogen, argon gas, or the mist of one of nitrogen, argon gas and hydrogen, and the volume ratio of nitrogen or argon gas and hydrogen is 1: (10-0).
Advantage of the present invention is:
1, the present invention at first prepares electrode material, subsequently electrode material is evenly mixed with quantity of organic, and the method through cold moudling is with its briquet again.Subsequently the block that presses is obtained containing the loose structure block of a large amount of electrode material powder through low sintering method, perhaps simultaneously the method through chemical vapour deposition (CVD) with the LiFePO of loose structure
4Particle surface coats the even continuous conductive carbon film of one deck and obtains the more excellent block electrode of conductivity.The prepared block electrode that goes out of the present invention only contains a large amount of active materials and a spot of conductive agent, therefore can avoid in experimentation owing to measure the experimental error that the balance inaccuracy is brought.
2, the inventive method is not used organic binder bond, need not the solvent of dissolved adhesive, and need not to use metal collector, therefore can save cost greatly.
3, technical process of the present invention and simple has been simplified the manufacture process of electrode, so has further reduced the manufacturing cost of electrode.
4, therefore the inventive method block electrode that can use nano-electrode material to prepare to contain the different size pore structure can significantly improve the chemical property of block electrode.
5, the electrode of the present invention's preparation does not use organic bond, and specific discharge capacity is high than the traditional preparation process method.And the prepared block electrode tool high power capacity that goes out, characteristics such as high-energy-density.
6, through the prepared porous blocks electrode that goes out of the inventive method, after electrochemistry circulation several times, electrolyte can contact with active material fully, so the chemical property that is drawn is accurate.
In a word; Adopt the block electrode conductivuty of this method preparation good, in the unit volume electrode charge/discharge capacity and specific capacity is high, preparation technology is simple, block electrode low cost of manufacture; And improved the chemical property of block electrode and the preparation flow that has shortened traditional handicraft greatly, solved conventional preparation LiFePO
4The operation of positive plate redundant and complicated needs the problem of the solvent of kinds of processes equipment and expensive adhesive and dissolved adhesive.On this basis, having solved traditional sign uses the membrane type electrode to characterize LiFePO
4The coarse problem of positive electrode chemical property.
Description of drawings
Fig. 1 is that the present invention and conventional process flow compare.Wherein, (a) be conventional process flow; (b) be technological process of the present invention.
Fig. 2 is porous, electrically conductive LiFePO among the embodiment 1
4The stereoscan photograph of block electrode shows that the block electrode is cellular and even pore distribution.
Fig. 3 is embodiment 1 resulting porous, electrically conductive LiFePO
4The transmission photo of anodal piece.
Fig. 4 is that the block electrode of embodiment 1 carries out: (a) nitrogen adsorption desorption curve and (b) pressure mercury analysis.
Battery that Fig. 5 is assembled for the block electrode of embodiment 1 is under different cycle-indexes: (a) Nyquist figure and (b) the impedance graph of a relation of bearing two/first power with frequency.
Fig. 6 is the block electrode electro Chemical performance of embodiment 1: (a) charging and discharging curve under the different electric stream mode and (b) cycle performance.
Fig. 7 is the block electrode electro Chemical performance of embodiment 2: (a) charging and discharging curve under the different electric stream mode and (b) cycle performance.
Fig. 8 is the block electrode electro Chemical performance of embodiment 3: (a) charging and discharging curve under the different electric stream mode and (b) cycle performance.
Fig. 9 (a)-(b) is the stereoscan photograph of block among the embodiment 4, shows that the block electrode that method synthesized through embodiment 4 demonstrates a fairly large number of mesopore (a) and macroporous structure (b).
Figure 10 is the chemical property of block electrode among the embodiment 4: (a) charging and discharging curve under the different electric stream mode and (b) cycle performance.
Embodiment
Embodiment 1:
Choose the 6.69g Lithium hydroxide monohydrate, be dissolved in the 30mL water.After treating that dissolving is accomplished, add 4mL phosphoric acid (concentration is 85wt%), generate Li this moment to it
3PO
4Suspension-turbid liquid.After question response is accomplished, add 0.225g ascorbic acid and 14.6g ferrous sulfate heptahydrate, finally form blue slurry to it.In mixture, introduce 20mL polyethylene glycol (200) subsequently again, make the polyethylene glycol (200) and the volume ratio of water remain 2: 4.Blue slurry is transferred to rapidly in the sealed reactor 180 ℃ of hydro-thermal reactions 1 hour.Separate then, obtain single-phase LiFePO
4In the present embodiment, LiFePO
4The particle diameter of powder is 50-500nm.
Get the dry LiFePO that crosses
4Powder 2g evenly mixes in grinding with the 1g citric acid.Subsequently the dried powder that mixes will be placed on cold moudling in the mould of Φ 8mm, the pressure of colding pressing is 100MPa, and the time of colding pressing is 30 seconds.Be placed into the flat-temperature zone of tube furnace to the block after the moulding, vacuumize half an hour (vacuum degree reaches about 10Pa) then, discharge the air in the stove after; Feed the mist of high-purity argon gas (bulk purity >=99.999%) and hydrogen again; The volume ratio of argon gas and hydrogen is 1: 0.03, be warming up to 350 ℃ after constant temperature carried out draining in 1 hour and handle, the water that makes the citric acid pyrolysis go out is fully discharged; Form loose structure simultaneously; The technical parameter of loose structure: porosity 58.8%, have macroporous structure, central hole structure and microcellular structure, the volume fraction of whole pore volumes that macroporous structure is shared is 41%; The volume fraction of whole pore volumes that central hole structure is shared is 42%, and all the other are microcellular structure; Macroporous structure aperture 90nm-3 μ m, central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.Constant temperature carried out sintering processes in 30 minutes after end temperature rose to 700 ℃, simultaneously can be so that RESEARCH OF PYROCARBON has more excellent electrical conductance.Feed acetylene gas subsequently, and continue insulation 30 minutes, wrap carbon and handle at 700 ℃.After treating that temperature retention time finishes, sample cools to room temperature with the furnace, takes out and obtains porous, electrically conductive LiFePO
4Block electrode (Fig. 2).
The quality of this block electrode and volume be not for having reached～52.7mg and～50mm
3And the active material particle of forming this block electrode is sintered bond each other, and has～conductive carbon film (Fig. 3) of the continuous homogeneous of 3nm.Through to LiFePO
4The block electrode adsorbs holder to be attached and presses the mercury analysis, draws LiFePO
4The block electrode exists macropore and central hole structure, and porous nickel is distributed in the block electrode (Fig. 4).Make positive pole with this block electrode, use lithium metal, be assembled into 2032 button cells, this battery is carried out ac resistance analysis after different recurrent states as GND.The result is to have obtained tangible lifting on the lithium ion diffusion coefficient or the electronic conductance of electrode after showing that (Fig. 5) is through the primary electrochemical circulation, but circulation then changes little again.Expression can make electrolyte infiltrate into electrode interior fully through once circulating through the block electrode that this method synthesized.With this battery constant current charge-discharge under the 0.443mA electric current, this porous, electrically conductive LiFePO
4The block electrode has good charge and discharge platform, and (Fig. 6 a).Discharge capacity is that conventional method prepares more than 100 times of the measured battery capacity of pole piece up to 8.22mAh first.And specific capacity has also reached the 158mAh/g that approaches theoretical capacity.Explanation has high capacity and specific capacity according to the prepared electrode of this method, and measured data are accurate.When increasing to 0.886mA along with electric current, the discharge capacity first of this block electrode is to have reached 7.97mAh, and specific capacity has also reached 153mAh/g.Fig. 6 b is the chemical property of this block electrode under the different electric stream mode.Can know that by figure this electricity block electrode shows electrochemistry cycle performance preferably under the current status of 0.443mA and 0.886mA.
Embodiment 2:
Be synthetic LiFePO with embodiment 1 difference
4Do not add polyethylene glycol (200) in the process.But making water fully as reaction medium, the amount of institute's water is 60mL.Other conditions all are same as embodiment 1, in the present embodiment, and porosity 61%; Have macroporous structure, central hole structure and microcellular structure; The volume fraction of whole pore volumes that macroporous structure is shared is 46%, and the volume fraction of whole pore volumes that central hole structure is shared is 43%, and all the other are microcellular structure; Macroporous structure aperture 90nm-5 μ m, central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.
Can know that by Fig. 7 a under 0.425mA constant current charge-discharge condition, this discharge capacity of the cell is up to 7.24mAh, and specific capacity also reaches 144mAh/g.Explanation has high capacity and specific capacity according to the prepared electrode of this method, and measured data are accurate.When increasing to 0.851mA along with electric current, the discharge capacity first of this block electrode has still reached 6.91mAh, and specific capacity has also reached 138mAh/g.This battery does not have obviously decay (Fig. 7 b) after having experienced 20 circulations.Embody through the prepared block electrode that goes out of this method and have excellent cycle performance.
Be synthetic LiFePO with embodiment 1 difference
4The amount of adding polyethylene glycol (200) in the process is different.
Polyethylene glycol: the volume ratio of water is 1: 1, and other conditions all are same as embodiment 1.In the present embodiment, porosity 56.5% has macroporous structure, central hole structure and microcellular structure, and the volume fraction of whole pore volumes that macroporous structure is shared is 39%, and the volume fraction of whole pore volumes that central hole structure is shared is 46%, and all the other are microcellular structure; Macroporous structure aperture 80nm-2 μ m, central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.
Can know that by Fig. 8 a under 0.425mA constant current charge-discharge condition, this discharge capacity of the cell is up to 7.36mAh, and specific capacity also reaches 147mAh/g.Explanation has high capacity and specific capacity according to the prepared electrode of this method, and measured data are accurate.When increasing to 0.851mA along with electric current, the discharge capacity first of this block electrode has still reached 7.25mAh, and specific capacity has also reached 145mAh/g.This battery does not have obviously decay (Fig. 8 b) after having experienced 20 circulations.
Be that with embodiment 1 difference the pore creating material that is added is a melamine.
Other conditions all are same as embodiment 1.In the present embodiment; The technical parameter of loose structure: porosity 68.1%, have macroporous structure, central hole structure and microcellular structure, the volume fraction of whole pore volumes that macroporous structure is shared is 47%; The volume fraction of whole pore volumes that central hole structure is shared is 45%, and all the other are microcellular structure; Macroporous structure aperture 50nm-10 μ m, central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.
Can be known by Fig. 9, be pore creating material through selecting melamine for use, can produce macroporous structure at the block electrode.Can know that by Figure 10 a under 0.432mA and 0.863mA constant current charge-discharge condition, this discharge capacity of the cell is up to 8.28mAh, and specific capacity also reaches 163mAh/g.Explanation has high capacity and specific capacity according to the prepared electrode of this method, and measured data are accurate.When increasing to 1.725mA along with electric current, the discharge capacity first of this block electrode has still reached 7.41mAh, and specific capacity has also reached 146mAh/g.This battery does not have obviously decay (Figure 10 b) after having experienced 15 circulations.This instance explanation; Compare with citric acid; Through using melamine to contain pore structure, therefore make electrolyte get into the inside of block electrode smoothly, thereby further improve the charge-discharge magnification performance of block electrode than horn of plenty as the prepared block electrode of pore creating material.
Embodiment result shows that the present invention can prepare porous, electrically conductive LiFePO under the situation of solvent that does not use any adhesive, dissolved adhesive and collector
4The block electrode.Adopt the block electrode conductivuty of this method preparation good, density is high, and the charge/discharge capacity of block electrode and specific capacity height.Technology of the present invention is simple, the low cost of manufacture of block electrode, and shortened the preparation flow of traditional handicraft greatly, solved conventional preparation LiFePO
4The technology of positive plate redundant and complicated, need kinds of processes equipment and expensive adhesive, the solvent of dissolved adhesive and the problem of collector.And the characteristics that have the amount of high active material in its unit volume make it when characterizing the chemical property of electrode material, have many characteristics such as very accurate.
Claims (10)
1. a lithium ion battery is used porous LiFePO
4The preparation method of block electrode is characterized in that, its concrete steps are following:
(1) synthesizes electrode material LiFePO
4Powder mixes powder with the organic substance pore creating material subsequently uniformly, and organic substance accounts for the 0wt%-90wt% of mixture gross mass, with the dried powder that mixes cold moudling in mould;
Said organic substance is a kind of or two or more mixture of citric acid, melamine, urea-formaldehyde resin, saccharomycete, glucose, sucrose, maltose;
(2) block of forming is put into the flat-temperature zone of tube furnace, fed protective gas after discharging furnace air subsequently, carried out draining in constant temperature 10-60 minute after then being warming up to design temperature 200-400 ℃ to handle and form loose structure; After temperature rises to 500-800 ℃ subsequently, carried out sintering processes in constant temperature 10-180 minute.
2. use porous LiFePO according to the described lithium ion battery of claim 1
4The preparation method of block electrode is characterized in that: said step (2) feeds carbon-source gas and carries out chemical vapour deposition (CVD) afterwards, is forming the LiFePO of loose structure
4Particle surface evenly coats one deck conductive carbon and obtains porous, electrically conductive LiFePO
4The block electrode.
3. use porous LiFePO according to the described lithium ion battery of claim 2
4The preparation method of block electrode is characterized in that: the thickness of conductive carbon is: 1-100nm.
4. use porous LiFePO according to claims 2 described lithium ion batteries
4The preparation method of block electrode is characterized in that: the carbon-source gas percent by volume is 1-20%, 500-800 ℃ of chemical vapour deposition (CVD) temperature, sedimentation time 10 minutes-3 hours; Post-depositional sample naturally cools to room temperature with stove, takes out to obtain porous, electrically conductive LiFePO
4The block electrode.
5. use porous LiFePO according to claims 2 described lithium ion batteries
4The preparation method of block electrode is characterized in that: carbon-source gas is acetylene or propylene.
6. use porous LiFePO according to claims 1 described lithium ion battery
4The preparation method of block electrode is characterized in that: in the said step (2), tube furnace is horizontal type stove or shaft (tower) furnace.
7. use porous LiFePO according to claims 1 described lithium ion battery
4The preparation method of block electrode is characterized in that: in the said step (2), the mode of discharging furnace air and water vapour is for vacuumizing or use inert gas purge.
8. use porous LiFePO according to claims 1 described lithium ion battery
4The preparation method of block electrode is characterized in that: in the said step (2), protective gas is one of nitrogen, argon gas, or the mist of one of nitrogen, argon gas and hydrogen, and the volume ratio of nitrogen or argon gas and hydrogen is 1: (10-0).
9. use porous LiFePO according to claims 1 described lithium ion battery
4The preparation method of block electrode; It is characterized in that: in the said step (2); The technical parameter of loose structure: porosity 10%-99% has macroporous structure, central hole structure and microcellular structure, and the volume fraction of whole pore volumes that macroporous structure is shared is 1%-99%; The volume fraction of whole pore volumes that central hole structure is shared is 1%-99%, and all the other are microcellular structure; Macroporous structure aperture 50nm-500 μ m, central hole structure aperture 2-50nm, the microcellular structure aperture is less than 2nm.
10. use porous LiFePO according to claims 1 described lithium ion battery
4The preparation method of block electrode is characterized in that: in the said step (1), the pressure 1-500MPa that colds pressing colds pressing time 1-6000 second.
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| CN110800135B (en) * | 2017-07-04 | 2022-08-30 | 株式会社Lg新能源 | Electrode and lithium secondary battery comprising the same |
| CN108258199A (en) * | 2018-01-19 | 2018-07-06 | 河北力滔电池材料有限公司 | LiFePO4 composite pole piece and preparation method |
| CN108258199B (en) * | 2018-01-19 | 2020-09-01 | 河北力滔电池材料有限公司 | Lithium iron phosphate composite pole piece and preparation method thereof |
| CN110858641A (en) * | 2018-08-22 | 2020-03-03 | 比亚迪股份有限公司 | Positive electrode material of lithium ion battery, preparation method of positive electrode material and lithium ion battery |
| CN110858641B (en) * | 2018-08-22 | 2021-04-20 | 比亚迪股份有限公司 | Positive electrode material of lithium ion battery, preparation method of positive electrode material and lithium ion battery |
| CN113991070A (en) * | 2021-09-14 | 2022-01-28 | 陕西创普斯新能源科技有限公司 | Lithium iron phosphate composite material and preparation method and application thereof |
| CN115159589A (en) * | 2021-09-23 | 2022-10-11 | 贵州振华新材料有限公司 | Lithium ion battery anode material, preparation method and application |
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