CN100376608C - Production of positive material of lithium battery - Google Patents
Production of positive material of lithium battery Download PDFInfo
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- CN100376608C CN100376608C CNB2005100964898A CN200510096489A CN100376608C CN 100376608 C CN100376608 C CN 100376608C CN B2005100964898 A CNB2005100964898 A CN B2005100964898A CN 200510096489 A CN200510096489 A CN 200510096489A CN 100376608 C CN100376608 C CN 100376608C
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a preparation method of positive material of lithium batteries. The present invention is characterized in that the method can replace linear polymer and elemental sulfur which are mixed in a mechanical method or a layer spreading method in normal temperature and pressure, the mixture is arranged in a glass or ceramic reaction tube. The reaction tube is arranged in a temperature control heating furnace with the outside temperature of 100 DEG C to 450 DEG C, after 0.5 to 10 hours of reaction, the reaction tube is taken out for natural cooling, and users can obtain charcoal grey solid powder carbon sulfur material after mechanical milling, scouring and vacuum drying. The present invention replaces the mixing of the linear polymer and the elemental sulfur in normal temperature and pressure and prepares the carbon sulfur material in one step via the heating reaction, and the present invention makes use of the thermal decomposition property of replacing the linear polymer and the effumability of sulfur. Therefore, the present invention avoids using any additional shield gas in reaction processes and has the advantages of low cost, simple preparation process, high specific capacity, high safety, etc.
Description
Technical field
The invention belongs to the battery technology field, particularly relate to a kind of preparation method who is used as the carbon sulfur materials of anode material of lithium battery.
Background technology
High tension battery is the vitals of mobile communication, power truck and new and high technology weapon, and the specific storage, the low excessively bottleneck of the present secondary battery positive electrode material specific storage of solution that improve its positive electrode material are one of gordian techniquies.Carbon sulphur polymkeric substance is one of the highest research object of present specific storage, influences the work-ing life of battery but its main chain is easy to depolymerization when discharge.Carbyne polysulfide class material is the positive electrode material that development in recent years has high energy storage prospect faster, such material is for being the skeleton main chain with carbon carbon, the sulfuration macromolecular material that forms at side chain introducing sulphur sulphur chain, solve the depolymerization problem of sulfur-containing molecules effectively, thereby should have bigger superiority.The preparation employing of carbyne polysulfide material at first prepares carbyne and carries out sulfurized method and hydrogeneous polyalkenyl halides and the elemental sulfur step reacting by heating preparation method under protection of inert gas again.Hydrogeneous polyalkenyl halides is the heat-labile polymkeric substance of a class, the time is easy to decompose in heating, produces hydrogen halide and stays the polymkeric substance that contains the unsaturated link(age) structure.In the two step method preparation process of carbyne polysulfide material, at first the thermal degradation preparation under protection of inert gas of hydrogeneous polyalkenyl halides material is contained the intermediate of carbyne structure, then with elementary sulfur prepared in reaction carbyne polysulfide material.In the direct reaction of hydrogeneous polyalkenyl halides material and elementary sulfur, also must make blanketing with inert gas.Because the thermal decomposition characteristic of hydrogeneous polyalkenyl halides, not only can be at direct reaction under the heating condition with elementary sulfur, and also the decomposition gas that is produced can directly need not additionally to add shielding gas as shielding gas.
Summary of the invention
The objective of the invention is provides a kind of preparation method of lithium cell carbon sulphur positive electrode material for overcoming disadvantages of background technology.The distinguishing feature of this method is to mix at normal temperatures and pressures with elementary sulfur to replace simple linear polymer, through reacting by heating one step preparation carbon sulfur materials, and can not use any shielding gas that adds in reaction process.The thermolysis that replaces simple linear polymer loses small molecules such as hydrogen halide and elementary sulfur and can replace unitary substitution reaction to simple linear polymer and carry out synchronously.Carbon atom on the main polymer chain skeleton and sulphur or many sulphur form covalent linkage, simultaneously, also form covalent linkage between the sulphur sulphur, as its energy-storage units.Because the sulphur sulfur molecule segment of energy storage all links to each other with backbone c atoms, therefore, helps avoiding the dissolving in electrolytic solution in charge and discharge process of sulfur-bearing small molecules, thereby helps improving the utilization ratio of system cycle performance and active substance.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of anode material of lithium battery, it is characterized in that this method is: will replace that simple linear polymer mechanically mixes at normal temperatures and pressures with elementary sulfur or layering is sprawled mode and mixed, mixture is placed glass or ceramic reaction tubes, and reaction tubes is placed outside temperature is 100 ℃～450 ℃ temperature control process furnace, react after 0.5～10 hour, take out naturally cooling, after mechanical disruption, washing and vacuum-drying, get grey black look pressed powder carbon sulfur materials; Described replacement simple linear polymer main chain is made up of carbon atom, and substituting group is not in the inside of molecular backbone chain, and substituting group is F, Cl, Br, I and above-mentioned substituent combination thereof; And in each polymer repeat unit, substituting group can be one or more than one.
The reaction system that the present invention relates to is an open system, utilizes the thermal decomposition characteristic of replacement simple linear polymer and the easy volatile of sulphur, and reaction process can not used any shielding gas that adds, and the atmosphere that utilizes reaction system self to be produced is shielding gas; Described replacement simple linear polymer mixes with elementary sulfur after reacting by heating one step preparation carbon sulfur materials; The blending ratio of described replacement simple linear polymer and elementary sulfur is a benchmark to replace simple linear polymer main chain carbon content, and carbon compares for being less than or equal to 2: 1 with the atomicity of sulphur; The form of described elementary sulfur is sublimed sulphur, crystallization sulphur or linear sulphur.
The carbon sulfur materials for preparing among the present invention is as the active substance of lithium battery anode, this anodal preparation method is: carbon sulfur materials, conductive agent, binding agent are reconciled into pasty state with solvent and coat on the aluminium foil, form through vacuum-drying, wherein: a, carbon sulfur materials are for preparing through the heating single step reaction with replacing simple linear polymer and elementary sulfur, this substituting group that replaces simple linear polymer is not in the inside of molecular backbone chain, and substituting group is F, Cl, Br, I and above-mentioned substituent combination thereof; And in each polymer repeat unit, substituting group can be one or more than one; B, conductive agent can be acetylene black, graphite, carbon fiber and other any electroconductibility powder; C, binding agent can be polyethylene oxide PEO, polytetrafluoroethylene PTFE or other suitable binding agent such as LA132 etc.
The lithium cell that the present invention relates to is that negative pole, barrier film and the electrolytic solution of positive pole, metallic lithium or the lithium alloy of active substance is formed by the carbon containing sulfur materials, and wherein: a, electrolyte lithium salt are lithium perchlorate, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, trifluoromethane sulfonic acid imido lithium etc.; B, solvent are tetrahydrofuran (THF) and derivative thereof, dioxolane, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbonate, propylene carbonate, benzene,toluene,xylene etc.
The present invention compared with prior art has the following advantages: the present invention adopts the replacement simple linear polymer to mix at normal temperatures and pressures with elementary sulfur; through reacting by heating one step preparation carbon sulfur materials; and in reaction process, can not use any shielding gas that adds, have with low cost, advantage such as preparation technology is simple, specific storage is high and security is good.
Description of drawings
The head that the process that Fig. 1 describes by embodiment 8 for the present invention is assembled into lithium cell is put curve.
The head that the process that Fig. 2 describes by embodiment 9 for the present invention is assembled into lithium cell is put curve.
Fig. 3 is the circulation discharge characteristic of 14505 type lithium celies of the embodiment of the invention 10 descriptions.
Embodiment
Get 5.0 gram polyvinylidene chloride and 15.0 gram sublimed sulphurs, place glass reaction tube, and Glass tubing is placed outside temperature is 250 ℃ temperature control process furnace, react after 3.5 hours, take out naturally cooling, soak sample and be transferred in the agate milling tank with a small amount of water-ethanol (1: 3), in 250 rev/mins grinding in ball grinder 6.5 hours.Use water-ethanol (1: 3) washing successively, washing with acetone, 140 mesh sieves are crossed in 60 ℃ of vacuum-dryings, get 15.0 gram grey black look solid carbon sulfur materials powder, yield 75.0%.
Embodiment 2
In glass reaction tube, stack 10.0 gram polyvinylidene chloride successively, 30.0 gram sublimed sulphur, 10.0 gram polyvinylidene chloride, 30.0 gram sublimed sulphur, 10.0 gram polyvinylidene chloride and 30.0 gram sublimed sulphurs, form sandwich type structural, and Glass tubing is placed outside temperature is 250 ℃ temperature control process furnace, react after 6.0 hours, take out naturally cooling, soak sample and be transferred in the agate milling tank with a small amount of water-ethanol (1: 3), in 250 rev/mins grinding in ball grinder 6.5 hours, use water-ethanol (1: 3) washing successively, washing with acetone, 140 mesh sieves are crossed in 60 ℃ of vacuum-dryings, get 98.0 gram grey black look solid carbon sulfur materials powder, yield 81.7%.
Get 7.0 gram polyvinylidene chloride and 7.0 gram sublimed sulphurs, place glass reaction tube, and Glass tubing is placed outside temperature is 250 ℃ ± 2 ℃ temperature control process furnace, react after 3.5 hours the taking-up naturally cooling.Soak sample and be transferred in the agate milling tank with a small amount of water-ethanol (1: 3),, use water-ethanol (1: 3) washing successively in 250 rev/mins grinding in ball grinder 6.5 hours, washing with acetone, 140 mesh sieves are crossed in 60 ℃ of vacuum-dryings, get 8.9 gram black solid carbon sulfur materials powder, yield 63.6%.
Embodiment 4
Get 2.00 gram polyvinylidene chloride and 4.00 gram sublimed sulphurs, place glass reaction tube, and Glass tubing is placed outside temperature is 150 ℃ temperature control process furnace, react after 10.0 hours the taking-up naturally cooling.Soak sample and be transferred in the agate milling tank with a small amount of water-ethanol (1: 3), in 250 rev/mins grinding in ball grinder 7.0 hours, use water-ethanol (1: 3) washing successively, washing with acetone, 60 ℃ of vacuum-dryings, cross 140 mesh sieves, get 5.05 gram grey black solid carbon sulfur materials powder, yield 84.2%.
Embodiment 5
Get 1.20 gram polyvinylidene chloride and 3.60 gram sublimed sulphurs, place glass reaction tube, and Glass tubing is placed outside temperature is 450 ℃ temperature control process furnace, react after 0.5 hour the taking-up naturally cooling.Soak sample and be transferred in the agate milling tank with a small amount of water-ethanol (1: 3),, use water-ethanol (1: 3) washing successively in 250 rev/mins grinding in ball grinder 6.5 hours, washing with acetone, 140 mesh sieves are crossed in 60 ℃ of vacuum-dryings, get 3.11 gram black solid carbon sulfur materials powder, yield 64.8%.
Embodiment 6
With the carbon sulfur materials 0.495g of embodiment 1 preparation, acetylene black 0.281g adds water 2ml after mixing with binding agent (LA132) 0.292g that contains 15% solid substance, fully is milled into no bubble thick slurry, and roll-in method is coated on the aluminium foil.60 ℃ of following vacuum-dryings were cut into the circular pole piece of 1.0cm2 more than 24 hours after the drying at room temperature, wherein activity substance content in the pole piece solid substance: 60.4%; Thickness (by active substance): 5.3 ± 0.8mg/cm
2
Embodiment 7
With the carbon sulfur materials 0.582g of embodiment 2 preparations, acetylene black 0.354g adds water 2ml after mixing with binding agent (LA132) 0.373g that contains 15% solid substance, fully is milled into no bubble thick slurry, and roll-in method is coated on the aluminium foil.60 ℃ of following vacuum-dryings were cut into the circular pole piece of 1.0cm2 more than 24 hours after the drying at room temperature, wherein activity substance content in the pole piece solid substance: 58.7%; Thickness (by active substance): 4.2 ± 0.4mg/cm
2
mg/cm2。
Embodiment 8
Pole piece with embodiment 6 preparations is a positive pole, and metallic lithium foil is a negative pole, and polypropylene film is a barrier film, and electrolytic solution is 1.2mol/L LiClO4 non-aqueous solution, and wherein solvent is 40%1,3-dioxolane+40% tetrahydrofuran (THF)+20% glycol dimethyl ether (volume ratio).After being assembled into battery, at stopping potential 2.9～1.6V, current density 0.3mA/cm
2Condition under discharge and recharge experiment.Head is put and is compared 997mAh/g.
Embodiment 9
Pole piece with embodiment 7 preparations is a positive pole, and metallic lithium foil is a negative pole, and polypropylene film is a barrier film, and electrolytic solution is 1.2mol/L LiClO4 non-aqueous solution, and wherein solvent is 40%1,3-dioxolane+40% tetrahydrofuran (THF)+20% glycol dimethyl ether (volume ratio).After being assembled into battery, at stopping potential 2.9～1.6V, current density 0.3mA/cm
2Condition under discharge and recharge experiment.Head is put specific storage 962mAh/g.
Pole piece with embodiment 7 preparations is a positive pole, and metallic lithium foil is a negative pole, and polypropylene film is a barrier film, and electrolytic solution is 1.2mol/L LiClO4 non-aqueous solution, and wherein solvent is 40%1,3-dioxolane+40% tetrahydrofuran (THF)+20% glycol dimethyl ether (volume ratio).After being assembled into 14505 type batteries,, carry out the cycle charge-discharge experiment under the condition of current density 80mA at stopping potential 2.9～1.6V.Circulate specific discharge capacity after 60 times greater than 300mAh/g.
Claims (4)
1. the preparation method of an anode material of lithium battery, it is characterized in that this method is: will replace that simple linear polymer mechanically mixes at normal temperatures and pressures with elementary sulfur or layering is sprawled mode and mixed, mixture is placed glass or ceramic reaction tubes, and reaction tubes is placed outside temperature is 100 ℃～450 ℃ temperature control process furnace, react after 0.5～10 hour, take out naturally cooling, after mechanical disruption, washing and vacuum-drying, get grey black look pressed powder carbon sulfur materials; Described replacement simple linear polymer main chain is made up of carbon atom, and substituting group is not in the inside of molecular backbone chain, and substituting group is F, Cl, Br, I and above-mentioned substituent combination thereof; And in each polymer repeat unit, substituting group can be one or more than one.
2. the preparation method of a kind of anode material of lithium battery according to claim 1, the blending ratio that it is characterized in that described replacement simple linear polymer and elementary sulfur is a benchmark to replace simple linear polymer main chain carbon content, and carbon compares for being less than or equal to 2: 1 with the atomicity of sulphur.
3. the preparation method of a kind of anode material of lithium battery according to claim 1 is characterized in that utilizing the thermal decomposition characteristic of replacement simple linear polymer and the easy volatile of sulphur, and the atmosphere that utilizes reaction system self to be produced is shielding gas.
4. the preparation method of a kind of anode material of lithium battery according to claim 1, the form that it is characterized in that described elementary sulfur is sublimed sulphur, crystallization sulphur or linear sulphur.
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| CNB2005100964898A CN100376608C (en) | 2005-12-13 | 2005-12-13 | Production of positive material of lithium battery |
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| CNB2005100964898A CN100376608C (en) | 2005-12-13 | 2005-12-13 | Production of positive material of lithium battery |
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| CN1817920A CN1817920A (en) | 2006-08-16 |
| CN100376608C true CN100376608C (en) | 2008-03-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339839A (en) * | 2001-09-21 | 2002-03-13 | 中国科学院上海冶金研究所 | Positive electrode material of organic sulphide for electrochemical power source and its prepn |
| CN1387271A (en) * | 2001-05-17 | 2002-12-25 | 中国人民解放军防化研究院第一研究所 | Carbyne polysulfide and lithium battery using it as positive electrode |
| CN1564369A (en) * | 2004-03-29 | 2005-01-12 | 天津大学 | Secondary lithium cell using sulfurized crosslinking PVC as cathode material |
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2005
- 2005-12-13 CN CNB2005100964898A patent/CN100376608C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387271A (en) * | 2001-05-17 | 2002-12-25 | 中国人民解放军防化研究院第一研究所 | Carbyne polysulfide and lithium battery using it as positive electrode |
| CN1339839A (en) * | 2001-09-21 | 2002-03-13 | 中国科学院上海冶金研究所 | Positive electrode material of organic sulphide for electrochemical power source and its prepn |
| CN1564369A (en) * | 2004-03-29 | 2005-01-12 | 天津大学 | Secondary lithium cell using sulfurized crosslinking PVC as cathode material |
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| CN1817920A (en) | 2006-08-16 |
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