CN104600335A - Carbon-fluoride-based primary lithium battery and preparation method and detection method thereof - Google Patents
Carbon-fluoride-based primary lithium battery and preparation method and detection method thereof Download PDFInfo
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- CN104600335A CN104600335A CN201510022734.4A CN201510022734A CN104600335A CN 104600335 A CN104600335 A CN 104600335A CN 201510022734 A CN201510022734 A CN 201510022734A CN 104600335 A CN104600335 A CN 104600335A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
- H01M6/5083—Testing apparatus
Abstract
The invention relates to a carbon-fluoride-based primary lithium battery and a preparation method and a detection method thereof. A battery positive plate consists of a conductive metal foil or net serving as a current collector and composite slurry attached to the conductive metal foil or net, wherein the composite slurry comprises carbon fluoride; and the electrolyte consists of nonaqueous electrolyte and an added functional additive used for improving the rate capability of the battery at least. The preparation method comprises the following steps: preparing the electrolyte, preparing positive and negative plates and assembling the battery. The carbon-fluoride-based primary lithium battery and the preparation method and the detection method thereof disclosed by the invention have the advantages that the electrolyte with the functional additive in the battery can be directly contacted with the positive plate, so that the plate has good interfacial properties; the battery has low interface resistance, the wetting property of the electrolyte is improved, and the transmission of lithium ions on the interface is improved, so that the rate capability of the carbon-fluoride-based primary lithium battery is improved; and moreover, a positive active material carbon fluoride or a carbon fluoride modified material and the electrolyte have good interfacial compatibility, so that good voltage platform and specific discharge capacity can be obtained.
Description
Technical field
The present invention relates to one and fluoridize carbon back lithium primary battery and preparation method thereof and detection method, be the long nonaqueous electrolytic solution stored of a kind of high magnification fluoridize carbon back lithium primary battery, belong to cell art.
Background technology
The theoretical specific capacity of lithium fluorocarbon battery is up to 865mAh/g, and open circuit voltage is 3.2-3.7V, temperature applicable range wide (-40 to 130 DEG C).Because its capacity density is apparently higher than the lithium primary battery such as lithium-manganese dioxide, lithium-thionyl chloride, and reach more than 10 years, the advantage such as environmentally friendly storage life, lithium fluorocarbon battery has a wide range of applications at security field, industrial circle, field of medicaments.As far back as the 1970's, lithium fluorocarbon battery just realizes commercialization, is the lithium battery of commercial applications the earliest in the world, but still not having large-scale batch production in world wide so far, be because its high rate performance is poor, and price is higher.Wherein high rate performance difference is the principal element that restriction lithium fluorocarbon battery is applied in powerful power consumption equipment.The chemical reaction of lithium fluorocarbon battery when discharging is: CFx+xLi → C+xLiF.The inorganic matter lithium fluoride (LiF) that fluorocarbons constantly generates insulation in the process of electric discharge and the carbon that can conduct electricity.Discharge chemistry reaction occurs on the three phase boundary of electrolyte, LiF, fluorocarbons.Therefore, the migration rate of the contact interface of electrolyte and fluorocarbons, the migration rate of lithium ion on interface, product is the key factor affecting battery discharge multiplying power.Interface between improvement electrolyte and fluorocarbons active material, the migration rate accelerating lithium ion and discharge product improves the effective means of high rate performance, but the additive much improving interface performance but brings the decline of battery capacity.The discharge-rate of the power consumption equipment of current fluorocarbons battery extensive use, all at below 0.05C, seldom has the commercial cells higher than 1C high power discharge.
Summary of the invention
The object of the invention is to, provide one to fluoridize carbon back lithium primary battery and preparation method thereof and detection method.Its electrolyte of described battery contains functional additive Triton X-100, when the electrolyte in battery and positive electrode material can be made to infiltrate, there is good interface performance, there is low cell interface resistance, significantly improve the wettability of electrolyte, improve the transmission of lithium ion in solid liquid interface, thus improve the high rate performance fluoridizing carbon back lithium primary battery; Positive active material fluorocarbons or fluorocarbon-modified material and electrolyte have good interface compatibility, thus obtain better voltage platform and specific discharge capacity, be a kind of working stability, efficiency is high, equipment dynamic battery that cost is low and portable electric appts power supply.
One of the present invention fluoridizes carbon back lithium primary battery technical scheme:
One fluoridizes carbon back lithium primary battery, comprises positive plate, negative plate, and barrier film and electrolyte; Described positive plate be by as collector conductive metal foil or net and be attached to conductive metal foil or online composite mortar is formed; Described composite mortar comprises fluorocarbons, or fluorocarbons is material modified; Described negative plate is made up of material modified or containing lithium metal the alloy material of lithium metal or lithium metal; Described electrolyte is the electrolyte with functional additive, comprise nonaqueous electrolytic solution and wherein add at least for improving the functional additive of battery high rate performance; Described functional additive content in the electrolytic solution counts 0.01% ~ 10% with percent by volume; Described functional additive has Triton X-100 (Trition 100, (C2H4O) nC14H22O) at least.
Further technical scheme of fluoridizing carbon back lithium primary battery of the present invention is:
Described fluoridizes carbon back lithium primary battery, and functional additive is Triton X-100 (Trition 100, (C2H4O) nC14H22O), and content in the electrolytic solution counts 0.01% ~ 1% with percent by volume.
Described fluoridizes carbon back lithium primary battery, and described functional additive also has SEI film forming agent, anti-over-charging additive, fire retardant and stabilizer one or more the composition in them.
Described fluoridizes carbon back lithium primary battery, described SEI film forming agent be vinylene carbonate (VC), fluorinated ethylene ester (FEC), chloroethylenes ester (ClEC), propane sultone (PS), butane sultones, tetraalkyl-dialkylene siloxanes, to vinyl benzene sulphonyl, per-fluoroalkyl sulfonyl and inferior amine salt one or more the mixture in them.
Described fluoridizes carbon back lithium primary battery, and described nonaqueous electrolytic solution is that lithium salts and organic solvent are mixed.
Described fluoridizes carbon back lithium primary battery, and described lithium salts is lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, di-oxalate lithium borate, the sub-acid amides lithium of bis trifluoromethyl sulfonic acid and trifluoromethyl sulfonic acid lithium, two fluorine sulfimide lithium, lithium perchlorate one or more the composition in them.
Described fluoridizes carbon back lithium primary battery, and described organic solvent is cyclic carbonate, chain linear carbonate, carboxylate, annular lactone one or more the mixed solvent in them.
The present invention is a kind of fluoridizes the purposes of carbon back lithium primary battery as electrokinetic cell and portable electric appts power supply, comprises for weaponry, electric tool, smart camera, and peak load regulation network, distribution power station, back-up source and communication base station.
Technical scheme of fluoridizing the preparation method of carbon back lithium primary battery of the present invention is:
Fluoridize a preparation method for carbon back lithium primary battery, comprise the steps:
Step one, prepare electrolyte:
First, in the glove box under room temperature state, prepare organic solvent, then add lithium salts in organic solvent, obtain nonaqueous electrolytic solution, then in nonaqueous electrolytic solution, adding functional additive, stir, being for assembling the electrolyte fluoridizing carbon back lithium primary battery; Or after preparing organic solvent, then by first adding functional additive in organic solvent, and then the sequential system adding lithium salts is for electrolyte;
Step 2, prepare positive and negative plate:
First prepare composite mortar, then composite mortar is evenly attached to the conductive metal foil or online as collector, then dry, obtain positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal;
Step 3, assembled battery:
Step 2 positive plate is after drying put into dry environment, then perforated membrane is placed between positive plate and negative plate, add the electrolyte that step one prepares, make positive plate and negative electrode plate complete wetting, be assembled into and fluoridize carbon back lithium primary battery.
The further technical scheme that the present invention fluoridizes the preparation method of carbon back lithium primary battery is:
The described preparation method fluoridizing carbon back lithium primary battery, step is as follows:
Step one: prepare electrolyte:
First, organic solvent is prepared in the glove box under room temperature state, by propene carbonate (PC, C5H7O6) with glycol dimethyl ether (DME, C4H10O2) solvent is with after volume ratio 1:1 mixing, lithium salts LiBF4 (LiBF4) is added again in organic solvent, be made into the nonaqueous electrolytic solution that LiBF4 (LiBF4) concentration is 1 mol/L, then in nonaqueous electrolytic solution, add the Triton X-100 (Trition 100 that percent by volume is 0.1%, (C2H4O) nC14H22O) functional additive, stir, be for assembling the electrolyte fluoridizing carbon back lithium primary battery,
Step 2, prepare positive and negative plate:
First using the N as fluorinated carbon material (CFx) and the carbon black of active material, Kynoar (PVDF), N-dimethyl pyrrolidone (NMP) solution mixes, make uniform composite mortar, the thickness be evenly attached to by composite mortar again as collector is the conducting metal aluminium foil or online of 15 μm, then dry under 60 DEG C of low temperature, be 50 μm by gained film thickness again, tight at 1MPa × 1cm2 pressure, then continue to dry 8 hours at high temperature 100 DEG C; Finally gained pole piece being cut into area is that the disk of 1cm2 is as positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal;
Step 3, assembled battery:
Step 2 positive plate is after drying put into argon gas glove box, again polypropylene porous film (Celgard 2300) is placed between positive plate and negative plate, the electrolyte that instillation step one prepares, makes positive plate and negative electrode plate complete wetting, is assembled into and fluoridizes carbon back lithium primary battery.
The detection method of what preparation method of the present invention obtained fluoridize carbon back lithium primary battery, comprises the steps:
A, on testing impedance equipment, carry out ac impedance measurement to fluoridizing carbon back lithium primary battery: voltage amplitude is 5mV, and test condition is frequency range 105-0.01Hz, and voltage is open circuit voltage;
B, measure the contact angle of electrolyte and positive plate with contact angle measurement;
C, on auto charge and discharge instrument, carry out discharging current test to fluoridizing carbon back lithium primary battery: according to the theoretical capacity density 865mAh/g of fluorocarbons, the electric current of carbon back lithium primary battery is fluoridized when going out 2C electric discharge according to the Mass Calculation of fluorocarbons active material in each positive plate, carry out constant-current discharge, discharge from open circuit voltage, cut-ff voltage is 1.5 V, and probe temperature is 25 DEG C.
Accompanying drawing explanation
Fig. 1 of the present inventionly fluoridizes carbon back lithium primary battery structural principle schematic diagram;
Fig. 2 is the discharge current curves A1 fluoridizing carbon back lithium primary battery of one embodiment of the invention and the comparison diagram of the discharge current curves A2 of the prior art battery for contrasting;
Fig. 3 is the AC impedance curve B 1 of fluoridizing carbon back lithium primary battery of one embodiment of the invention and AC impedance curve B 2 comparison diagram of the prior art battery for contrasting;
Fig. 4 is the contact angle C1 of the electrolyte fluoridizing carbon back lithium primary battery of one embodiment of the invention and positive plate and the electrolyte of prior art battery for contrasting and the contact angle C2 comparison diagram of positive plate;
The above-mentioned prior art battery for contrasting is the battery not containing Triton X-100 (Trition 100, (C2H4O) nC14H22O) functional additive in electrolyte.
In Fig. 1: 1-positive plate; 1.1-conductive metal foil or net; 1.2-composite mortar; 2-electrolyte; 3-barrier film; 4-negative plate; In Fig. 2: the discharge current curves of A1-fluoridize carbon back lithium primary battery; The discharge current curves of A2-prior art battery; Fig. 3: B1-fluoridize the AC impedance curve of carbon back lithium primary battery; The AC impedance curve of B2-prior art battery; Fig. 4: C1-fluoridize the electrolyte of carbon back lithium primary battery and the contact angle of positive plate; C2-the electrolyte of prior art battery and the contact angle of positive plate.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details:
Embodiment 1, is as shown in Figure 1 a basic embodiment of fluoridizing carbon back lithium primary battery of the present invention.One fluoridizes carbon back lithium primary battery, comprises positive plate 1, negative plate 4, and barrier film 3 and electrolyte 2; Described positive plate 1 be by as collector conductive metal foil or net 1.1 and be attached to conductive metal foil or online composite mortar 1.2 is formed; Described composite mortar 1.2 comprises fluorocarbons, or fluorocarbons is material modified; Described negative plate 4 is made up of material modified or containing lithium metal the alloy material of lithium metal or lithium metal; Described electrolyte 2 for having the electrolyte of functional additive, comprise nonaqueous electrolytic solution and wherein add at least for improving the functional additive of battery high rate performance; The content of described functional additive in electrolyte 2 counts 0.01% ~ 10% with percent by volume; Described functional additive has Triton X-100 (Trition 100 at least, (C2H4O) nC14H22O), this functional additive is for improving the wettability of electrolyte to the positive plate made by fluorocarbons or fluorocarbon-modified material and negative plate, reduce the interface resistance fluoridizing carbon back lithium primary battery containing fluorocarbons or fluorocarbon-modified material, contribute to transporting and forming stable solid liquid interface of lithium ion, the high rate performance making the type fluoridize carbon back lithium primary battery significantly improves.
The present invention fluoridizes its structure of carbon back lithium primary battery and also has shell, and version has clasp formula, Soft Roll formula, box hat formula etc.Because shell mechanism form matches with applied equipment, therefore the shape of shell, size etc. are also different.
Embodiment 2, fluoridize carbon back lithium primary battery preferred embodiment for of the present invention.As different from Example 1, described fluoridizes carbon back lithium primary battery, and functional additive Triton X-100 (Trition 100, (C2H4O) nC14H22O) content in the electrolytic solution counts 0.01% ~ 1% with percent by volume.
Embodiment 3, be further embodiment on embodiment 1 basis.Described fluoridizes carbon back lithium primary battery, and described functional additive also has SEI film forming agent, anti-over-charging additive, fire retardant and stabilizer one or more the composition in them.
Embodiment 4, be further embodiment on embodiment 1 basis.Described fluoridizes carbon back lithium primary battery, described SEI film forming agent be vinylene carbonate (VC), fluorinated ethylene ester (FEC), chloroethylenes ester (ClEC), propane sultone (PS), butane sultones, tetraalkyl-dialkylene siloxanes, to vinyl benzene sulphonyl, per-fluoroalkyl sulfonyl and inferior amine salt one or more the mixture in them.Described nonaqueous electrolytic solution is that lithium salts and organic solvent are mixed.Described lithium salts is lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, di-oxalate lithium borate, the sub-acid amides lithium of bis trifluoromethyl sulfonic acid and trifluoromethyl sulfonic acid lithium, two fluorine sulfimide lithium, lithium perchlorate one or more the composition in them.Described organic solvent is cyclic carbonate, chain linear carbonate, carboxylate, annular lactone one or more the mixed solvent in them.
Embodiment 5, to fluoridize the purposes of carbon back lithium primary battery as electrokinetic cell and portable electric appts power supply for the present invention is a kind of, for weaponry, electric tool, smart camera can also be widely used in, and peak load regulation network, distribution power station, back-up source and communication base station.
Embodiment 6, the present invention fluoridize the basic embodiment of the preparation method of carbon back lithium primary battery.Fluoridize a preparation method for carbon back lithium primary battery, comprise the steps:
Step one, prepare electrolyte:
First, in the glove box under room temperature state, prepare organic solvent, then add lithium salts in organic solvent, obtain nonaqueous electrolytic solution, then in nonaqueous electrolytic solution, adding functional additive, stir, being for assembling the electrolyte fluoridizing carbon back lithium primary battery;
Also have a kind of execution mode to be: after preparing organic solvent, then by first adding functional additive in organic solvent, and then the sequential system adding lithium salts is for electrolyte, its result does not affect the performance of electrolyte;
Step 2, prepare positive and negative plate:
First prepare composite mortar, then composite mortar is evenly attached to the conductive metal foil or online as collector, then dry, obtain positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal; Step 3, assembled battery:
Step 2 positive plate is after drying put into dry environment, then perforated membrane is placed between positive plate and negative plate, add the electrolyte that step one prepares, make positive plate and negative electrode plate complete wetting, be assembled into and fluoridize carbon back lithium primary battery.
Embodiment 7, the present invention fluoridize a preferred embodiment of the preparation method of carbon back lithium primary battery.The described preparation method fluoridizing carbon back lithium primary battery, step is as follows:
Step one: prepare electrolyte:
First, organic solvent is prepared in the glove box under room temperature state, by propene carbonate (PC, C5H7O6) with glycol dimethyl ether (DME, C4H10O2) solvent is with after volume ratio 1:1 mixing, lithium salts LiBF4 (LiBF4) is added again in organic solvent, be made into the nonaqueous electrolytic solution that LiBF4 (LiBF4) concentration is 1 mol/L, then in nonaqueous electrolytic solution, add the Triton X-100 (Trition 100 that percent by volume is 0.1%, (C2H4O) nC14H22O) functional additive, stir, be for assembling the electrolyte fluoridizing carbon back lithium primary battery,
Step 2, prepare positive and negative plate:
First using the N as fluorinated carbon material (CFx) and the carbon black of active material, Kynoar (PVDF), N-dimethyl pyrrolidone (NMP) solution mixes, make uniform composite mortar, the thickness be evenly attached to by composite mortar again as collector is on the conducting metal aluminium foil of 15 μm, then dry under 60 DEG C of low temperature, be 50 μm by gained film thickness again, tight at 1MPa × 1cm2 pressure, then continue to dry 8 hours at high temperature 100 DEG C; Finally gained pole piece being cut into area is that the disk of 1cm2 is as positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal;
In the present embodiment, in positive plate, fluorinated carbon material (CFx) accounts for the 82wt% being attached to total composite mortar on conducting metal aluminium foil, and bonding agent accounts for 8wt%, and carbon black accounts for 10 wt%;
Step 3, assembled battery:
Step 2 positive plate is after drying put into argon gas glove box, again polypropylene porous film (Celgard 2300) is placed between positive plate and negative plate, the electrolyte that instillation step one prepares, makes positive plate and negative electrode plate complete wetting, is assembled into and fluoridizes carbon back lithium primary battery.
When making clasp formula fluoridizes carbon back lithium primary battery, the adjacent negative plate of negative pole column cap, the adjacent positive plate of positive pole column cap.
Embodiment 8, be the preferred embodiment fluoridizing the detection method that carbon back lithium primary battery detects obtained embodiment 7 preparation method, step is as follows:
A, on testing impedance equipment (CHI660, Shanghai occasion China), carry out ac impedance measurement to fluoridizing carbon back lithium primary battery: voltage amplitude is 5mV, and test condition is frequency range 105-0.01Hz, and voltage is open circuit voltage; As shown in Figure 3, B1 is the AC impedance curve fluoridizing carbon back lithium primary battery of embodiment 7, and B2 is the AC impedance curve of the prior art battery for contrasting;
B, use contact angle measurement (De Fei, Dataphysics) measure the contact angle of electrolyte and positive plate; As shown in Figure 4, C1 be embodiment 7 fluoridize the electrolyte of carbon back lithium primary battery and the contact angle of positive plate, C2 is the electrolyte of prior art battery for contrasting and the contact angle of positive plate;
C, at auto charge and discharge instrument (LAND, Wuhan Jin Nuo Science and Technology Ltd.) on carry out discharging current test to fluoridizing carbon back lithium primary battery: according to the theoretical capacity density 865mAh/g of fluorocarbons, the electric current of carbon back lithium primary battery is fluoridized when going out to discharge completely for 0.5 hour speed electric discharge (the namely 2C electric discharge) of theoretical capacity according to the Mass Calculation of fluorocarbons active material in each positive plate, carry out constant-current discharge, discharge from open circuit voltage, cut-ff voltage is 1.5 V, and probe temperature is 25 DEG C; As shown in Figure 2, A1 is the discharge current curves of fluoridizing carbon back lithium primary battery of embodiment 7, and A2 is the discharge current curves of the prior art battery for contrasting.
From accompanying drawing 2,3,4, the present invention fluoridizes carbon back lithium primary battery and has remarkable technique effect main as follows:
As shown in Figure 2: in discharge process, the present invention fluoridizes carbon back lithium primary battery (discharge current curves is A1), than for the prior art battery (discharge current curves is A2) contrasted, there is higher discharge platform, this shows: the present invention fluoridizes carbon back lithium primary battery and has less polarization phenomena when high magnification, and in electrolyte, lithium ion is better in the transport at interface.The specific discharge capacity that the present invention fluoridizes carbon back lithium primary battery is 689.4 mAh/g, and the specific discharge capacity of prior art battery is only 464.7 mAh/g.Therefore, the present invention fluoridizes carbon back lithium primary battery and under high magnification, has better discharge performance than prior art battery.
As shown in Figure 3: the present invention fluoridizes carbon back lithium primary battery (impedance curve is B1), than the prior art battery (impedance curve is B2) for contrasting, there is lower interface impedance and better interface performance.
As shown in Figure 4: the present invention fluoridizes carbon back lithium primary battery (contact angle of electrolyte and positive plate is C1), than the prior art battery (contact angle of electrolyte and positive plate is C2) for contrasting, there is less contact angle, this shows: the present invention fluoridizes carbon back lithium primary battery electrolyte and has better wettability than for the prior art battery electrolyte contrasted, lower interface energy.But, if the too high levels of Triton X-100 (Trition 100, (C2H4O) nC14H22O) functional additive, the conductivity of electrolyte can be made to decline; If content is too low, then effectively can not improve the wettability of electrolyte and lithium ion and transport performance at interface, thus the content of Triton X-100 (Trition 100, (C2H4O) nC14H22O) functional additive should in concentration range of the present invention.
The present invention has Triton X-100 (Trition 100, (C2H4O) nC14H22O) functional additive electrolyte fluoridize carbon back lithium primary battery, there is low cell interface resistance, electrolyte wherein and positive electrode have better wettability, effectively can promote and fluoridize carbon back fluorocarbons base lithium primary battery high rate performance, thus obtain better voltage platform and specific discharge capacity, can as electrokinetic cell and portable electric appts power supply etc.
Claims of the present invention is not limited to above-described embodiment.
Claims (11)
1. fluoridize a carbon back lithium primary battery, it is characterized in that, comprise positive plate, negative plate, and barrier film and electrolyte; Described positive plate be by as collector conductive metal foil or net and be attached to conductive metal foil or online composite mortar is formed; Described composite mortar comprises fluorocarbons, or fluorocarbons is material modified; Described negative plate is made up of material modified or containing lithium metal the alloy material of lithium metal or lithium metal; Described electrolyte is the electrolyte with functional additive, comprise nonaqueous electrolytic solution and wherein add at least for improving the functional additive of battery high rate performance; Described functional additive content in the electrolytic solution counts 0.01% ~ 10% with percent by volume; Described functional additive has Triton X-100 (Trition 100, (C at least
2h
4o) nC
14h
22o).
2. according to claim 1ly fluoridize carbon back lithium primary battery, it is characterized in that, functional additive is Triton X-100 (Trition 100, (C
2h
4o) nC
14h
22o), content in the electrolytic solution counts 0.01% ~ 1% with percent by volume.
3. according to claim 1ly fluoridize carbon back lithium primary battery, it is characterized in that, described functional additive also has SEI film forming agent, anti-over-charging additive, fire retardant and stabilizer one or more the composition in them.
4. according to claim 3ly fluoridize carbon back lithium primary battery, it is characterized in that, described SEI film forming agent be vinylene carbonate (VC), fluorinated ethylene ester (FEC), chloroethylenes ester (ClEC), propane sultone (PS), butane sultones, tetraalkyl-dialkylene siloxanes, to vinyl benzene sulphonyl, per-fluoroalkyl sulfonyl and inferior amine salt one or more the mixture in them.
5. according to claim 1ly fluoridize carbon back lithium primary battery, it is characterized in that, described nonaqueous electrolytic solution is that lithium salts and organic solvent are mixed.
6. according to claim 5ly fluoridize carbon back lithium primary battery, it is characterized in that, described lithium salts is lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, di-oxalate lithium borate, the sub-acid amides lithium of bis trifluoromethyl sulfonic acid and trifluoromethyl sulfonic acid lithium, two fluorine sulfimide lithium, lithium perchlorate one or more the composition in them.
7. according to claim 5ly fluoridize carbon back lithium primary battery, it is characterized in that, described organic solvent is cyclic carbonate, chain linear carbonate, carboxylate, annular lactone one or more the mixed solvent in them.
8. a claim 1 to 7 fluoridizes the purposes of carbon back lithium primary battery as electrokinetic cell and portable electric appts power supply described in any one, comprise for weaponry, electric tool, smart camera, and peak load regulation network, distribution power station, back-up source and communication base station.
9. claim 1 to 7 fluoridizes a preparation method for carbon back lithium primary battery described in any one, it is characterized in that, comprises the steps:
Step one, prepare electrolyte:
First, in the glove box under room temperature state, prepare organic solvent, then add lithium salts in organic solvent, obtain nonaqueous electrolytic solution, then in nonaqueous electrolytic solution, adding functional additive, stir, being for assembling the electrolyte fluoridizing carbon back lithium primary battery; Or after preparing organic solvent, then by first adding functional additive in organic solvent, and then the sequential system adding lithium salts is for electrolyte;
Step 2, prepare positive and negative plate:
First prepare composite mortar, then composite mortar is evenly attached to the conductive metal foil or online as collector, then dry, obtain positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal;
Step 3, assembled battery:
Step 2 positive plate is after drying put into dry environment, then perforated membrane is placed between positive plate and negative plate, add the electrolyte that step one prepares, make positive plate and negative electrode plate complete wetting, be assembled into and fluoridize carbon back lithium primary battery.
10. the preparation method fluoridizing carbon back lithium primary battery according to claim 9, it is characterized in that, step is as follows:
Step one: prepare electrolyte:
First, in the glove box under room temperature state, prepare organic solvent, by propene carbonate (PC, C
5h
7o
6) and glycol dimethyl ether (DME, C
4h
10o
2) solvent with after volume ratio 1:1 mixing, then in organic solvent, add lithium salts LiBF4 (LiBF
4), be made into LiBF4 (LiBF
4) concentration is the nonaqueous electrolytic solution of 1 mol/L, in nonaqueous electrolytic solution, then add the Triton X-100 (Trition 100, (C that percent by volume is 0.1%
2h
4o) nC
14h
22o) functional additive, stirs, and is for assembling the electrolyte fluoridizing carbon back lithium primary battery;
Step 2, prepare positive and negative plate:
First using the N as fluorinated carbon material (CFx) and the carbon black of active material, Kynoar (PVDF), N-dimethyl pyrrolidone (NMP) solution mixes, make uniform composite mortar, the thickness be evenly attached to by composite mortar again as collector is on the conducting metal aluminium foil of 15 μm, then dry under 60 DEG C of low temperature, it is 50 μm by gained film thickness again, at 1MPa × 1cm
2pressure is tight, then continues to dry 8 hours at high temperature 100 DEG C; Finally gained pole piece being cut into area is 1cm
2disk as positive plate; Negative plate is made with material modified or containing lithium metal the alloy material of lithium metal or lithium metal;
Step 3, assembled battery:
Step 2 positive plate is after drying put into argon gas glove box, again polypropylene porous film (Celgard 2300) is placed between positive plate and negative plate, the electrolyte that instillation step one prepares, makes positive plate and negative electrode plate complete wetting, is assembled into and fluoridizes carbon back lithium primary battery.
The detection method of fluoridizing carbon back lithium primary battery that 11. 1 kinds of claim 10 preparation methods obtain: it is characterized in that, comprise the steps:
A, on testing impedance equipment, carry out ac impedance measurement to fluoridizing carbon back lithium primary battery: voltage amplitude is 5mV, and test condition is frequency range 10
5-0.01Hz, voltage is open circuit voltage;
B, measure the contact angle of electrolyte and positive plate with contact angle measurement;
C, on auto charge and discharge instrument, carry out discharging current test to fluoridizing carbon back lithium primary battery: according to the theoretical capacity density 865mAh/g of fluorocarbons, the electric current of carbon back lithium primary battery is fluoridized when going out 2C electric discharge according to the Mass Calculation of fluorocarbons active material in each positive plate, carry out constant-current discharge, discharge from open circuit voltage, cut-ff voltage is 1.5 V, and probe temperature is 25 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098247A (en) * | 2015-07-15 | 2015-11-25 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of primary lithium battery and primary lithium battery |
| CN107078312A (en) * | 2015-06-03 | 2017-08-18 | 日立麦克赛尔株式会社 | Nonaqueous electrolytic solution one-shot battery and its manufacture method |
| CN109119602A (en) * | 2018-06-29 | 2019-01-01 | 浙江工业大学 | A kind of preparation method of the porous wooden carbon modified metal lithium titanate cathode material |
| CN112993289A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Lithium/carbon fluoride battery, electrolyte thereof and use method thereof |
| CN114628671A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Carbon fluoride material, preparation and application |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107078312A (en) * | 2015-06-03 | 2017-08-18 | 日立麦克赛尔株式会社 | Nonaqueous electrolytic solution one-shot battery and its manufacture method |
| CN107078312B (en) * | 2015-06-03 | 2021-05-04 | 麦克赛尔控股株式会社 | Non-aqueous electrolyte primary battery and method for manufacturing same |
| CN105098247A (en) * | 2015-07-15 | 2015-11-25 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of primary lithium battery and primary lithium battery |
| CN105098247B (en) * | 2015-07-15 | 2019-02-15 | 深圳新宙邦科技股份有限公司 | Disposable lithium-battery nonaqueous electrolytic solution and disposable lithium-battery |
| CN109119602A (en) * | 2018-06-29 | 2019-01-01 | 浙江工业大学 | A kind of preparation method of the porous wooden carbon modified metal lithium titanate cathode material |
| CN109119602B (en) * | 2018-06-29 | 2020-10-02 | 浙江工业大学 | Preparation method of porous charcoal modified metal lithium negative electrode material |
| CN112993289A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Lithium/carbon fluoride battery, electrolyte thereof and use method thereof |
| CN114628671A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Carbon fluoride material, preparation and application |
| CN114628671B (en) * | 2020-12-11 | 2023-11-07 | 中国科学院大连化学物理研究所 | Fluorocarbon material and preparation and application thereof |
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