CN1252849C - Organic sulfide positive pole for thin film battery and its prepn - Google Patents

Organic sulfide positive pole for thin film battery and its prepn Download PDF

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CN1252849C
CN1252849C CNB011268344A CN01126834A CN1252849C CN 1252849 C CN1252849 C CN 1252849C CN B011268344 A CNB011268344 A CN B011268344A CN 01126834 A CN01126834 A CN 01126834A CN 1252849 C CN1252849 C CN 1252849C
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organic
preparation
positive pole
polymer
anode
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CN1337753A (en
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王久林
解晶莹
杨军
徐乃欣
晏莉琴
杜柯
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Metallurgy of CAS
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to a novel anode used for a thin film battery and a preparing method thereof, which belongs to the field of batteries and is characterized in that the anode is prepared from organic sulfide which has electrochemical activity, high energy density and high capacity density. The preparing method comprises: organic polymers are dissolved in solvent, the solution is uniformly spread on a current collector, and then, the solution reacts with sulfur vapor at 200 to 400 DEG C to obtain the anode for a thin film battery, or the organic polymers are dissolved in solvent and are uniformly mixed with elemental sulfur, and then, the mixture is sulfurized at 200 to 400 DEG C to obtain the anode. The sulfur content of the material is from 40 to 90 wt%. The anode capacity density of a thin film battery prepared from the anode is from 500 to 900 mAh/g. The preparing method si characterized in that the anode for a thin film battery and the active organic sulfide used in the anode are simultaneously prepared.

Description

The preparation method of the organic sulfide positive pole that a kind of hull cell is used
Technical field
The present invention relates to a kind of novel hull cell preparation method of anodal and this novel anode, this positive pole has mainly adopted a kind of organic sulfide polymer of electro-chemical activity.
Background technology
Along with the continuous development of process technology in modern age, MEMS (micro electro mechanical system) (Micro ElectromechanicalSystem is called for short MEMS) becomes a new technical field and industry.For example; The machine butterfly of the automobile of Micropump, micro motor, the 3mm size that can start, the aircraft of 2cm size and flight and can enter human vas and carry out microrobot of diagnostic work etc.The appearance of this emerging technology field and industry has proposed many brand-new challenges also for traditional electric power system.Thus, hull cell and even more small energy resource system technology are arisen at the historic moment.
Hull cell generally is made up of six parts: 1 protective layer; 2 negative poles; 3 solid electrolytes; 4 positive poles; 5 collectors; 6 matrixes.The preparation section of conventional films anode is roughly as follows:
Elder generation's sputter collector on matrix.Basis material can be semiconductor silicon, aluminium, glass or polyester.The requirement of concrete basis material is by the requirement decision of actual needs and manufacture craft, more precisely by anodal selection decision.Collector plays the electron conduction effect, can be Ti, Pt, Al, or other electronic conductor.In order to improve adhesion between collector and matrix, also can be on matrix first sputter one deck Ti as adhesive linkage [J.Electrochem.Soc., 2001,148 (4): A318].
On collector, make anodal again.Concrete manufacture method is by the different activities material decision of adopting.Positive active material can be V 2O 5, TiS 2, LiMn 2O 4, LiCoO 2Or LiNiO 2Even also can adopt different manufacture crafts with a kind of active material.People such as K.West have adopted three kinds of diverse ways to make V 2O 5The active material hull cell, be respectively radio frequency sputtering (Radio Frequency, RF), physical vapour deposition (PVD) (Physical Vapour Deposition, PVD) and solvent method [J.Power Sources, 1993,43-44:127].It is very big that the positive active material that adopts the RF method to make is influenced by oxygen partial pressure in the sputter gas, and partial pressure of oxygen is high more, and cycle performance is good more, but high keto sectional pressure makes sputtering rate very slow; The V of PVD preparation 2O 5Be close-packed structure, this structure can be destroyed in cyclic process, the cycle performance variation; Adopt solvent method, the V of the sol-gel process of saying so more accurately preparation 2O 5Major defect is to contain the crystallization water, needs heat treatment, and performance was suitable with the RF method after strictness dewatered, and is only easy operating of RF and cheap alternative method.
B.Wang has studied in great detail and has used LiCoO 2Hull cell [J.Eletrochem.Soc., 1992,139:1845] as positive active material.The cycle performance of battery is very good, and each capacity attenuation is only between 0.0001-0.002%, thereby cycle life is greater than 10000 times.Decision LiCoO 2The principal element of cycle performance is the structure of active material, the LiCoO of well-crystallized attitude 2Has good cycle performance.But crystallization process is very complicated, the LiCoO of sputtering forming 2Need heat-treat: be warming up to 500-700 ℃ with 5 ℃/min speed and keep 2h down, reduce to room temperature with 1 ℃/min speed then.For LiMn 2O 4Equally need be 400 ℃ of following heat treatments.Adopt to need heat treated positive active material to require matrix high temperature resistant, and when needing to consider heat treatment between layers of material in conjunction with problem.
Be confined to traditional positive electrode such as V from the positive maximum of the above battery of current thin film as can be seen more 2O 5, TiS 2, LiMn 2O 4, LiCoO 2Or LiNiO 2The specific capacity of the more various positive electrodes of table 1 and price.Though elemental sulfur has the highest cost performance, be generally primary cell by the battery of its making, organic sulfur compound is the highest material of a kind of cost performance in chargeable battery, and can not cause environmental pollution.Current thin film anode preparation method complexity, to the equipment requirements height, the present invention has proposed a kind of simple hull cell anode preparation method in conjunction with the preparation characteristic and the conventional films cell production process of organic sulfide polymer this electro-chemical activity, that have high capacity density and high-energy-density.
Various positive electrode specific energies of table 1 and price comparison
Material Theoretical specific capacity (mAh/g) Voltage (V) Actual specific capacity (mAh/g) The relative price prediction
LiCoO 2 275 3.7 130-140 1
LiNiO 2 274 3.4 170-180 0.86
LiMn 2O 4 148 3.8 100-120 0.17
V 2O 5 400 2.5 200-300
S m 1675 2.1 400-800 0.017
DMcT 376 3.2 160-220 0.26
(CS x) n (sulfur-bearing 50wt%) 837.5 2.0 500-900 0.035
Polyaniline 294 3.7 80-90 1.38
Annotate:
1, DMcT is 2,5-dimercapto, 1,3,4-thiadiazoles;
2, the relative price shown in this table is with LiCoO 2The per kilogram material price is 1 relative price ratio.
Summary of the invention
The invention discloses a kind of novel hull cell positive pole and preparation method thereof.This positive pole has mainly adopted a kind of organic sulfide polymer of electro-chemical activity.The preparation method comprises organic polymer is dissolved in the solvent, solution is evenly coated on the collector, then at 150-400 ℃ of positive pole that obtains hull cell down with the sulphur steam reaction, perhaps organic polymer is dissolved in the solvent and with elemental sulfur and evenly mixes, obtain positive pole 150-400 ℃ of following vulcanizing treatment then, sulfur content is 40-90wt% in the material.Utilize its positive electrode capacity density of hull cell of this material preparation can reach 500-900mAh/g.
Positive pole of the present invention comprises collector and electroactive substance two parts.
Collector works to compile electric current in hull cell, can be multiple electronic conductor, and for example: carbon net, copper mesh, nickel foam, aluminium net also can be copper pool, nickel pool, aluminium pool.Different collectors will produce bigger influence to the performance of hull cell.
The active material that the present invention adopts is a kind of electro-chemical activity, have the organic sulfide polymer of high capacity density and high-energy-density, the application of relevant this novel organic sulfur compound separate case, now briefly introduce as followsly, the polymer monomer structural formula of this kind novelty is following one or more:
Figure C0112683400061
S in the formula mRepresent many sulphur functional group, be the electro-chemical activity functional group of the organic sulfide polymer of this high capacity density and high-energy-density, m is the integer of 2-8.R 1And R 2It is the functional group that influences this Material Physics and chemical property.R 1And R 2At least a being selected from :-S m,-CH 3,-Cl ,-F ,-CH 2Cl ,-CHCl 2,-CH 2F ,-CHF 2, phenyl.Being connected with covalent bond between S and the S in the molecule, formation is similar to-structure of S-S-; Be with-S between S and the S m-the class polyacetylene main chain backbone of two or more conductions is coupled together.
Consider the conventional films cell production process and in conjunction with the preparation characteristic of organic sulfide polymer this electro-chemical activity, that have high capacity density and high-energy-density, a kind of novel anode preparation method has been proposed, the positive pole that it is characterized in that hull cell carries out in the lump with the preparation of the anodal active material that is adopted, finish simultaneously, concrete preparation process is as follows:
(a) sputter one deck collector on basis material, basis material can be silicon chip or glass;
(b) take by weighing a certain amount of organic polymer or title plastics, the form of this polymer can be powder, fractionlet, particle or small column;
(c) with the organic polymer in the organic solvent dissolution step (b);
(d) solution in the step (c) is coated on step (a) collector;
(e) collector in the step (d) is placed in the inert environments, puts into an elemental sulfur target simultaneously.Inert environments can be Ar or N 2
(f) heating makes the elemental sulfur distillation, and slowly volatilization takes place organic solvent simultaneously.Sulphur after the distillation and the organic polymer generation dehydrogenation vulcanization reaction in the solution generate organic sulfide polymer electro-chemical activity, that have high capacity density and high-energy-density and the hull cell described among the present invention and use anodal.
In addition, can be with the organic polymer in the organic solvent dissolution step (b) in step (c), add elemental sulfur or sublimed sulfur or high purity sulphur and evenly mixing again, the part by weight of organic polymer and elemental sulfur is 1: 1 to 1: 20 in the mixture, then step (e) can be saved, but heating makes the elemental sulfur distillation in the step (f), still needs inert environments, as Ar or N 2All the other are same as above.
Wherein the collector in the step (a) can be carbon net, copper mesh, nickel foam, aluminium net, also can be copper pool, nickel pool, aluminium pool, and different collectors will produce bigger influence to the performance of hull cell; The organic polymer that adopts in the step (b) can be a kind of in polypropylene (PP), polyvinyl dichloride, polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride, polyacrylonitrile (PAN), polystyrene, polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), the polymethyl methacrylate (PMMA), or the copolymer between them, or the copolymer between they and the polyethylene, also can be the mixture between them; The organic solvent that adopts in the step (c) is following a kind of or their mixture at least: acetonitrile, kerosene, acetone, ethanol, isopropyl alcohol, the tert-butyl alcohol, oxolane (THF), dimethyl formamide (DMF), methyl-sulfoxide (DMSO), propene carbonate (PC), diethyl carbonate (DEC), dipropyl carbonate (DMC), methyl pyrrolidone (NMP).
Used elemental sulfur or sublimed sulfur, purity are 99%; High purity sulphur purity is 99.9%.
Reaction temperature is controlled at 200-400 ℃, and the reaction time was controlled at 1-6 hour.
Because will produce a large amount of gases in the course of reaction, these gases may be H 2S, HCl or HF are so reaction needs to carry out in the device of strictness sealing.Constantly feed inert gas in the course of reaction, tail gas feeds in the alkaline solution.These alkaline solutions can be following one or more combination: NH 3H 2O, NaOH, KOH or Ca (OH) 2
In order to verify the chemical property of organic sulfide positive pole provided by the invention, the present invention has also prepared hull cell, anodal adopt above-mentioned organic sulfur compound, electrolyte adopts solid electrolyte, and negative pole can be metal or alloy such as Li, Li-Sn, Li-Si, Li-Al.Electrolyte plays the ionic conduction effect in battery, be clipped between positive pole and the negative pole, promptly plays the barrier film effect simultaneously.This solid electrolyte is at least by following a kind of composition the: Li 2O-B 2O 3-Li 2SO 4, Li 2S-SiS 2-P 2S 5, Li 2S-SiS 2-Li 3PO 4, LiI-Li 2S-SiS 2, Li 3.6Si 0.6P 0.4O 4, Li 3.3PO 3.9N 0.17LiI-Li 2S-SiS 2Has very high room-temperature ion conductance, Li 3.3PO 3.9N 0.17Have and the good interface stability of negative pole.
Anodal specific capacity reaches 500-900mAh/g in the hull cell that obtains thus, and average discharge volt is at 1.8-2.0V, and efficiency for charge-discharge is near 100%, and cycle performance is good.
Embodiment
Below by specific embodiment substantive distinguishing features of the present invention is described further, but the present invention is not limited only to these embodiment.
Embodiment 1
Take by weighing a certain amount of PEO particle, be dissolved in the acetonitrile, be made into solution.At Si sheet sputter layer of Ni collector.Solution is coated on the above-mentioned Ni sheet then.Put into the inert environments of using the Ar gas shiled together with the elemental sulfur target.Be heated to 250 ℃ and keep 5h down.The dehydrogenation vulcanization reaction takes place in the PEO in sublimed sulfur and the solution, and solvent volatilizees gradually and is rejected in the NaOH alkaline solution of subsequent treatment under this temperature.The organic sulfide polymer sulfur content that obtains thus is 46wt%.Its structural formula is a front monomer structure formula (IV).
Embodiment 2
Change the PEO among the embodiment 1 into the PVC polymer, be dissolved in the DMF solution, add elemental sulfur and evenly mixing then.At Si sheet sputter one deck Cu collector.Then above-mentioned solution is coated on the Cu sheet.Put into inert environments with the Ar gas shiled.Be heated to 350 ℃ and keep 1h down.The dehydrogenation vulcanization reaction also takes place with PVC in the solution, and solvent volatilizees gradually and is rejected in the KOH alkaline solution of subsequent treatment under this temperature in sulphur distillation.The organic sulfide polymer sulfur content that obtains thus is 80wt%.
Embodiment 3
(50: 50wt%), all the other are with embodiment 2 to change the PVC among the embodiment 2 into PVC and the poly mixture of PE.Obtain that sulfur content is 55wt% in the organic sulfur compound.
Embodiment 4
The positive pole that embodiment 2 is made moves into preparation solid electrolyte Li in the RF sputter 3.3PO 3.9N 0.17With negative pole lithium and encapsulation.Battery open circuit voltage is 2.5V, and anodal specific capacity is that efficiency for charge-discharge is near 100% about 600mAh/g.

Claims (4)

1, the preparation method of the organic sulfide positive pole used of a kind of hull cell is characterized in that the positive pole of hull cell and the preparation of the anodal active organic sulfur compound that is adopted finish simultaneously, and concrete preparation process is:
(a) sputter one deck collector on basis material;
(b) take by weighing a certain amount of organic polymer, the form of this polymer is powder, fractionlet, particle or small column; Described organic polymer is a kind of in polyvinyl dichloride, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyacrylonitrile, polystyrene, the polyethylene glycol oxide;
(c) with the polymer in the organic solvent dissolution step (b), add elemental sulfur and evenly mixing, the part by weight of organic polymer and elemental sulfur is 1: 1 to 1: 20 in the mixture;
(d) mixture in the above-mentioned steps (c) is coated on step (a) collector;
(e) collector in the step (d) is placed in the inert environments, inert environments is Ar or N 2
(f) heating makes the elemental sulfur distillation, slowly volatilization takes place in organic solvent simultaneously, and reaction temperature is controlled at 200-400 ℃, and the reaction time was controlled at 2-6 hour, organic polymer generation dehydrogenation vulcanization reaction in sulphur and the solution forms the organic sulfur compound of electro-chemical activity, finishes anodal preparation simultaneously.
2, preparation a kind of hull cell as claimed in claim 1 is with the method for organic sulfide positive pole, it is characterized in that described collector is a kind of in carbon net, copper mesh, nickel foam, aluminium net, Copper Foil, nickel foil, the aluminium foil; Matrix is silicon chip or sheet glass.
3,, it is characterized in that the organic solvent that adopts is following a kind of or their mixture at least: acetonitrile, kerosene, acetone, ethanol, isopropyl alcohol, the tert-butyl alcohol, oxolane, dimethyl formamide, methyl-sulfoxide, propene carbonate, diethyl carbonate, dipropyl carbonate, methyl pyrrolidone by the preparation method of the described hull cell of claim 1 with organic sulfide positive pole.
4, by the preparation method of the described hull cell of claim 1 with organic sulfide polymer positive pole, the purity that it is characterized in that used elemental sulfur or sublimed sulfur is 99%, and the purity of high purity sulphur is 99.9%.
CNB011268344A 2001-09-21 2001-09-21 Organic sulfide positive pole for thin film battery and its prepn Expired - Fee Related CN1252849C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022261642A1 (en) * 2021-06-08 2022-12-15 NOHMs Technologies, Inc. Silicon-sulfur-polymer based composite anodes for lithium-ion batteries

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WO2012040934A1 (en) * 2010-09-30 2012-04-05 Shanghai Jiao Tong University Cathode material for li-s battery and method for forming the same
CN103390767B (en) * 2012-05-11 2016-01-20 清华大学 Lithium ion battery
CN103050729A (en) * 2012-12-28 2013-04-17 大连理工大学 Lithium sulfur battery
CN110890543B (en) * 2018-09-10 2021-04-06 天津大学 Sustainable magnolol-sulfur copolymer as positive electrode active material of lithium-sulfur battery and preparation method
CN109950472B (en) * 2019-03-21 2020-11-24 华中科技大学 Lithium-sulfur battery positive electrode material, preparation method thereof, electrode plate and lithium-sulfur battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022261642A1 (en) * 2021-06-08 2022-12-15 NOHMs Technologies, Inc. Silicon-sulfur-polymer based composite anodes for lithium-ion batteries

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