CN102610862B - Preparation method for lithium battery taking polypyrrole-coated magnesium borate as anode material - Google Patents
Preparation method for lithium battery taking polypyrrole-coated magnesium borate as anode material Download PDFInfo
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- CN102610862B CN102610862B CN201210070819.6A CN201210070819A CN102610862B CN 102610862 B CN102610862 B CN 102610862B CN 201210070819 A CN201210070819 A CN 201210070819A CN 102610862 B CN102610862 B CN 102610862B
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Abstract
The invention relates to lithium battery preparation and aims to provide a preparation method for a lithium battery taking polypyrrole-coated magnesium borate as an anode material. The preparation method comprises the following steps of: respectively mixing and grinding N-methylpyrrolidone solution prepared from the polypyrrole-coated magnesium borate, acetylene black and polyvinylidene fluoride (PVDF) and N-methylpyrrolidone solution prepared from a lithium ion battery cathode material, the acetylene black and the PVDF; blending into a paste, and then, coating the paste to a copper film; drying the paste in the shade, and then performing compression moulding to obtain a cathode and an anode; and injecting electrolyte to obtain the lithium battery, wherein the electrolyte is characterized in that LiPF6 is taken as a solute, and a mixture of ethylene carbonate, carbonic acid and dimethyl carbonate is taken as a solvent. According to the preparation method for the lithium battery taking the polypyrrole-coated magnesium borate as the anode material, a high-capacity lithium ion battery anode material is formed by utilizing the characteristic of high lithium storage specific capacity of MgB2. The lithium battery has the advantages of high heat stability and good electrical conductivity, and thereby, the electrochemical dynamics performance of the cathode is improved, the electrode polarization is reduced, the speed capacity of the lithium battery is increased, and the potential of the cathode is smooth.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material and lithium ion battery thereof, particularly the coated boronation magnesium of polypyrrole and the preparation method as the lithium ion battery of negative material.
Background technology
The advantages such as that lithium ion battery has is lightweight, capacity large, memory-less effect, thereby obtained generally application.Present many digital equipments have all adopted lithium ion battery to make power supply.The energy density of lithium ion battery is very high, and its capacity is 1.5～2 times of Ni-MH battery of same weight, and there is very low self-discharge rate, containing advantages such as noxious substances, be not the major reason of its extensive use.The people such as nineteen ninety Japan Nagoura are developed into take petroleum coke as negative pole, with LiCoO
2for anodal lithium ion battery: LiC
6| LiClO
4-PC+EC|LiCoO
2.The same year.Moli and the large Battery Company of sony two are declared the lithium ion battery of releasing take carbon as negative pole.1991, Sony energy technology company and battery portion developed jointly a kind of lithium ion battery take glycan alcohol RESEARCH OF PYROCARBON (PFA) as negative pole.Lithium ion battery negative material has graphite (C
6), sulfide: TiS
2, NbS
2, oxide: WO
3, V
2o
5, SnO
2deng.Take graphite cathode material as example, negative reaction in charge and discharge process:
C
6+xLi
++xe＝＝Li
xC
6
When battery is charged, on the positive pole of battery, there is lithium ion to generate, the lithium ion of generation arrives negative pole through electrolyte movement.And be layer structure as the graphite of negative pole, and it has a lot of micropores, and the lithium ion that arrives negative pole is just embedded in the micropore of carbon-coating, forms lithium intercalation compound (Li
xc
6), the lithium ion of embedding is more, and charging capacity is higher.When battery is discharged, the lithium ion being embedded in graphite linings is deviate from, and positive pole is got back in motion again.Get back to anodal lithium ion more, discharge capacity is higher.
As the negative material of lithium battery, must be to possess following requirement: (1) lithium storage capacity is high; (2) embedding, the deintercalation reaction of lithium in negative material is fast, and the diffusion coefficient of lithium ion in solid phase is large, little in the mobile impedance at electrode-electric solution liquid interface; (3) existence of lithium ion in electrode material is stable; (4), in the charge and discharge cycles of battery, negative material change in volume is little; (5) electron conduction is high; (6) negative material does not dissolve in electrolyte.
The selection of negative material has a great impact the performance of battery.Cathode of lithium battery research and development at present mainly concentrates on material with carbon element and has the metal oxide of special construction.The most frequently used is graphite electrode, because graphitic conductive is good, degree of crystallinity is higher, has good layer structure, is applicable to the embedding-deintercalation of lithium.And its slotting lithium current potential is low and smooth, can be lithium ion battery high operating voltage is stably provided, be roughly: (vs.Li between 0.00～0.20V
+/ Li).Japanese honda company utilizes the thermal decomposition product PPP-700 of poly-phenylene vinylene (ppv) (Polyparaphenylene-PPP) (with PPP to 700 ℃ of certain firing rate heating, and be incubated the thermal decomposition product that certain hour obtains) as negative pole, reversible capacity can exceed LiC
6(372mAh g
-1).
Boronation magnesium (MgB
2) be a kind of ionic compound, crystal structure belongs to hexagonal crystal system.It is a kind of intercal type compound, magnesium layer and boron layer alternative arrangement.In temperature, slightly approach absolute temperature 40K (being equivalent to-233 ℃) and can change superconductor into.Its transition temperature is almost up to the twice of other superconductors of the same type, and its actual work temperature is 20～30K.At aspects such as superconducting magnet, power transmission line and sensitive magnetic field detectors, there is potential application foreground.
Polypyrrole is research and uses more a kind of heterocycle conjugated type conducting polymer, is generally unformed black solid.Take pyrroles as monomer, through the method for chemical polymerization or electrochemically oxidative polymerization, make conductive membrane.It can be ferric trichloride, ammonium persulfate, hydrogen peroxide etc. that the oxidant of chemical polymerization leads to.Pyrroles can be in acidic aqueous solution and multiple organic electrolyte can electrochemically oxidative polymerization film forming, the polymerizing conditions such as the character such as its conductivity and mechanical strength and electrolyte anion, solvent, pH value and temperature are closely related.Electric polypyrrole has conjugated chain oxidation, corresponding anion doped structure, and its conductivity can reach 102～103S/cm, and hot strength can reach 50～100MPa, has good electrochemical oxidation-reduction invertibity.In polymer, between pyrrole structure unit, mainly with α position, be coupled to each other, when at α substd, polymerization reaction can not be carried out.Electricity consumption chemical oxidative polymerization method can directly generate conductive membrane at electrode surface, and its conductivity can reach 102S/cm, and good stability is in polyacetylene.The oxidizing potential of polypyrrole, than the low about 1V of monomer whose left and right, is yellow, is brown after doping.Polypyrrole also can adulterate by chemical doping method, after doping, due to the introducing of counter ion, has certain ionic conduction ability.Polypyrrole is except using as electric conducting material, and as outside the occasions such as extraordinary electrode, also, for aspects such as electronical display materials, as linear polyenes, polypyrrole also has certain photoconductivity matter.
Summary of the invention
The technical problem to be solved in the present invention is, provides a kind of than the more coated boronation magnesium material of conductive film of height ratio capacity and the preparation method of the lithium battery take it as negative material of material with carbon element.
For technical solution problem, concrete scheme of the present invention is:
A kind of preparation method take the coated boronation magnesium of polypyrrole as the lithium battery of negative material is provided, comprises:
The preparation of negative pole: by 1-METHYLPYRROLIDONE (NMP) solution 85: 10: 100 mixed grindings in mass ratio of coated polypyrrole boronation magnesium, acetylene black, Kynoar (PVDF), be coated on copper film after being modulated into paste; After drying in the shade at 100Kg cm
-2pressure under compressing, obtain negative pole; In 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95;
Anodal preparation: by anode material for lithium-ion batteries: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, are coated on aluminium film after being modulated into paste; After drying in the shade at 100Kg cm
-2pressure under compressing, obtain positive pole; In 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95; Described anode material for lithium-ion batteries is LiCoO
2, LiNiO
2, LiMn
2o
4or LiFePO
4;
The assembling of battery: take microporous polypropylene membrane as barrier film, the electrode material side of anodal and negative pole is formed to sandwich structure with barrier film in opposite directions, inject electrolyte, obtain lithium battery; Electrolyte is with LiPF
6for solute, take the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate as solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in electrolyte
6concentration be 1mol L
-1.
In the present invention, the coated boronation magnesium of described polypyrrole prepares by following method:
(1) getting purity is 99.99% metal magnesium powder and boron powder, after evenly mixing, under the high-purity argon atmosphere of purity 99.999%, in 700～950 ℃ of temperature calcinings 1～4 hour, forms boronation magnesium dust by the mass ratio of 1: 1.125;
(2) take methanol aqueous solution or chloroform water solution as solvent, boronation magnesium dust is distributed in solvent and is made into suspension-turbid liquid, the mass ratio of boronation magnesium and solvent is 1: 10～1: 30; Adding glacial acetic acid to regulate pH value is 2～3, stirring at room 20～60min; Add pyrroles to stir 10～20min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 5～1: 1 again; Then add H
2o
2as the initator of polymerization reaction, 200W microwave heating 1～30min, pyrroles and H
2o
2mass ratio be 1: 0.05～0.5; Naturally after cooling, use deionized water washing and filtering, under vacuum condition, in 80～90 ℃, be dried 3～4h; At N
2inert atmosphere under 300～800 ℃ of insulation 1h heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole.
In the present invention, the mass concentration 20wt% of described methanol aqueous solution or chloroform water solution.
In the present invention with MgB
2as lithium cell cathode material, be can form respectively Li during according to this lithium cell charging
2mgB
2, lithium storage content is respectively 1168mAh g
-1, be current business-like graphite cathode material (372mAh g
-1) 3 times.MgB in charge and discharge process
2there is embedding lithium and the reaction of de-lithium:
MgB
2+2Li
++2e＝＝Li
2?MgB
2
In the present invention, polypyrrole is coated MgB
2as the negative material of lithium ion battery, because these intercalation materials of li ions are among electric polypyrrole film coated, the efflorescence that electrode material that disproportionated reaction causes occurs these intercalation materials of li ions in charging process is all controlled in the coated capsule of polypyrrole film and occurs, can not cause coming off of negative material, stablize the structure of negative pole, thereby improve the life-span of lithium ion battery.This point is showing particularly outstandingly aspect the high power charging-discharging cycle life of raising lithium ion battery.Up to now, not by MgB
2as the report of lithium ion battery negative material.
The beneficial effect that the present invention has:
The present invention utilizes MgB
2there is the characteristic of high storage lithium specific capacity, form a kind of lithium ion battery negative material of high power capacity.At MgB
2surface forms electric polypyrrole film and is conducive to the stable of electrode structure.Polypyrrole MgB of the present invention
2material has good thermal stability, the advantage of good conductivity, thus the electrochemical kinetics performance of raising negative pole reduces electrode polarization, improves the speed capabilities of lithium battery, and negative pole current potential is smooth, as shown in Figure 1.Can be applicable to the electrokinetic cell of electric automobile.
Accompanying drawing explanation
Fig. 1 is the coated MgB of polypyrrole prepared by embodiment mono-
2charging and discharging curve, charging and discharging currents is all 100mA/g.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment mono-: polypyrrole film is coated MgB
2preparation
After getting purity and be 99.99% metal magnesium powder and boron powder and evenly mixing by the mass ratio of 1: 1.125, under the high-purity argon atmosphere of purity 99.999%, temperature is calcined 4 hours at 700 ℃, forms boronation magnesium dust;
Boronation magnesium dust is distributed in solvent (methanol aqueous solution: 20wt%) and is made into suspension-turbid liquid, and the mass ratio of boronation magnesium and solvent is 1: 10; Adding glacial acetic acid to regulate pH value is 2, stirring at room 20min; Add pyrroles to stir 10min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 5 again; Add H
2o
2as the initator of polymerization reaction, 200W microwave heating 1min, pyrroles and H
2o
2mass ratio be 1: 0.05; Naturally cooling; With after deionized water washing and filtering, 80 ℃ of dry 3h of vacuum; At N
2the lower 300 ℃ of insulation 4h of inert atmosphere heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole.
Embodiment bis-: polypyrrole film is coated MgB
2for the lithium battery (1) of negative pole
After getting purity and be 99.99% metal magnesium powder and boron powder and evenly mixing by the mass ratio of 1: 1.125, under the high-purity argon atmosphere of purity 99.999%, temperature is calcined 3 hours at 800 ℃, forms boronation magnesium dust;
Boronation magnesium dust is distributed in solvent (chloroform water solution: 20wt%) and is made into suspension-turbid liquid, and the mass ratio of boronation magnesium and solvent is 1: 20; Adding glacial acetic acid to regulate pH value is 2.5, stirring at room 30min; Add pyrroles to stir 15min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 3 again; Add H
2o
2as the initator of polymerization reaction, 200W microwave heating 10min, pyrroles and H
2o
2mass ratio be 1: 0.1; Naturally cooling; With after deionized water washing and filtering, 85 ℃ of dry 3.5h of vacuum; At N
2the lower 400 ℃ of insulation 1h of inert atmosphere heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole.
By above-mentioned negative material: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on copper film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain the coated boronation magnesium negative pole of polypyrrole.
By anode material for lithium-ion batteries LiCoO
2: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on aluminium film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain LiCoO
2anodal.
Employing microporous polypropylene membrane is barrier film.The electrode material side of anodal and negative pole is formed to sandwich structure with barrier film in opposite directions, inject electrolyte, form lithium ion battery.Electrolyte is with LiPF
6for solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in electrolyte
6concentration be 1mol L
-1.
Embodiment tri-: polypyrrole film is coated MgB
2for the lithium battery (2) of negative pole
After getting purity and be 99.99% metal magnesium powder and boron powder and evenly mixing by the mass ratio of 1: 1.125, under the high-purity argon atmosphere of purity 99.999%, temperature is calcined 2 hours at 900 ℃, forms boronation magnesium dust;
Boronation magnesium dust is distributed in solvent (methanol aqueous solution: 20wt%) and is made into suspension-turbid liquid, and the mass ratio of boronation magnesium and solvent is 1: 30; Adding glacial acetic acid to regulate pH value is 3, stirring at room 60min; Add pyrroles to stir 20min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 1 again; Add H
2o
2as the initator of polymerization reaction, 200W microwave heating 30min, pyrroles and H
2o
2mass ratio be 1: 0.5; Naturally cooling; With after deionized water washing and filtering, 90 ℃ of dry 4h of vacuum; At N
2lower 800 ℃ of insulation 1 h of inert atmosphere heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole
By above-mentioned negative material: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on copper film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain the coated boronation magnesium negative pole of polypyrrole.
By anode material for lithium-ion batteries LiMn
2o
4: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on aluminium film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain LiMn
2o
4anodal.
Employing microporous polypropylene membrane is barrier film.The electrode material side of anodal and negative pole is formed to sandwich structure with barrier film in opposite directions, inject electrolyte, form lithium ion battery.Electrolyte is with LiPF
6for solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in electrolyte
6concentration be 1mol L
-1.
Embodiment tetra-: polypyrrole film is coated MgB
2for the lithium battery (3) of negative pole
After getting purity and be 99.99% metal magnesium powder and boron powder and evenly mixing by the mass ratio of 1: 1.125, under the high-purity argon atmosphere of purity 99.999%, temperature is calcined 1 hour at 950 ℃, forms boronation magnesium dust;
Boronation magnesium dust is distributed in solvent (chloroform water solution: 20wt%) and is made into suspension-turbid liquid, and the mass ratio of boronation magnesium and solvent is 1: 25; Adding glacial acetic acid to regulate pH value is 3, stirring at room 60min; Add pyrroles to stir 20min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 2 again; Add H
2o
2as the initator of polymerization reaction, 200W microwave heating 30min, pyrroles and H
2o
2mass ratio be 1: 0.5; Naturally cooling; With after deionized water washing and filtering, 90 ℃ of dry 4h of vacuum; At N
2the lower 800 ℃ of insulation 1h of inert atmosphere heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole.
By above-mentioned negative material: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on copper film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain the coated boronation magnesium negative pole of polypyrrole.
By anode material for lithium-ion batteries LiFePO
4: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, in 1-METHYLPYRROLIDONE (NMP) solution of vinylidene (PVDF), the mass ratio of PVDF and NMP is 5: 95.Be modulated into after paste, be coated on aluminium film, dry in the shade; At 100Kg cm
-2pressure under compressing, obtain LiFePO
4anodal.
Employing microporous polypropylene membrane is barrier film.The electrode material side of anodal and negative pole is formed to sandwich structure with barrier film in opposite directions, inject electrolyte, form lithium ion battery.Electrolyte is with LiPF
6for solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, the LiPF in electrolyte
6concentration be 1mol L
-1.
Finally, above announcement is only specific embodiments of the invention.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1. the preparation method take the coated boronation magnesium of polypyrrole as the lithium battery of negative material, is characterized in that, comprising:
The preparation of negative pole: by 1-METHYLPYRROLIDONE (NMP) solution 85: 10: 100 mixed grindings in mass ratio of coated polypyrrole boronation magnesium, acetylene black, Kynoar (PVDF), be coated on copper film after being modulated into paste; After drying in the shade at 100Kg cm
-2pressure under compressing, obtain negative pole; In 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), the mass ratio of PVDF and NMP is 5: 95;
Anodal preparation: by anode material for lithium-ion batteries: acetylene black: 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), 85: 10: 100 mixed grindings in mass ratio, are coated on aluminium film after being modulated into paste; After drying in the shade at 100Kg cm
-2pressure under compressing, obtain positive pole; In 1-METHYLPYRROLIDONE (NMP) solution of Kynoar (PVDF), the mass ratio of PVDF and NMP is 5: 95; Described anode material for lithium-ion batteries is LiCoO
2, LiNiO
2, LiMn
2o
4or LiFePO
4;
The assembling of battery: take microporous polypropylene membrane as barrier film, the electrode material side of anodal and negative pole is formed to sandwich structure with barrier film in opposite directions, inject electrolyte, obtain lithium battery; Electrolyte is with LiPF
6for solute, take the mixture of ethylene carbonate and dimethyl carbonate as solvent, ethylene carbonate: the mass ratio of dimethyl carbonate is 4: 6, the LiPF in electrolyte
6concentration be 1mol L
-1.
2. method according to claim 1, is characterized in that, the coated boronation magnesium of described polypyrrole prepares by following method:
(1) getting purity is 99.99% metal magnesium powder and boron powder, after evenly mixing, under the high-purity argon atmosphere of purity 99.999%, in 700～950 ℃ of temperature calcinings 1～4 hour, forms boronation magnesium dust by the mass ratio of 1: 1.125;
(2) take methanol aqueous solution or chloroform water solution as solvent, boronation magnesium dust is distributed in solvent and is made into suspension-turbid liquid, the mass ratio of boronation magnesium and solvent is 1: 10～1: 30; Adding glacial acetic acid to regulate pH value is 2～3, stirring at room 20～60min; Add pyrroles to stir 10～20min, wherein the mass ratio of pyrroles and boronation magnesium is 1: 5～1: 1 again; Then add H
2o
2as the initator of polymerization reaction, 200W microwave heating 1～30min, pyrroles and H
2o
2mass ratio be 1: 0.05～0.5; Naturally after cooling, use deionized water washing and filtering, under vacuum condition, in 80～90 ℃, be dried 3～4h; At N
2inert atmosphere under 300～800 ℃ of insulation 1h heat-treat, make the lithium ion battery negative material of the coated boronation magnesium of polypyrrole.
3. method according to claim 2, is characterized in that, the mass concentration 20wt% of described methanol aqueous solution or chloroform water solution.
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| CN111712953A (en) * | 2018-04-23 | 2020-09-25 | 株式会社村田制作所 | Lithium ion secondary battery |
| CN113394405B (en) * | 2021-05-24 | 2022-07-12 | 西安交通大学 | Preparation method of electrode coating for actively preventing thermal runaway of lithium ion battery |
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| CN102044674A (en) * | 2009-10-12 | 2011-05-04 | 中国科学院物理研究所 | Anode material for lithium ion battery and preparation method thereof |
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