CN106935743B - Lithium seawater battery and preparation method thereof - Google Patents
Lithium seawater battery and preparation method thereof Download PDFInfo
- Publication number
- CN106935743B CN106935743B CN201710195949.5A CN201710195949A CN106935743B CN 106935743 B CN106935743 B CN 106935743B CN 201710195949 A CN201710195949 A CN 201710195949A CN 106935743 B CN106935743 B CN 106935743B
- Authority
- CN
- China
- Prior art keywords
- lithium
- piece
- aluminum
- plastic
- diaphragm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 185
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000013535 sea water Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920003023 plastic Polymers 0.000 claims abstract description 119
- 239000004033 plastic Substances 0.000 claims abstract description 119
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 95
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 92
- 238000004806 packaging method and process Methods 0.000 claims abstract description 83
- 239000003792 electrolyte Substances 0.000 claims abstract description 76
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 65
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 65
- 239000004743 Polypropylene Substances 0.000 claims abstract description 22
- 229920001155 polypropylene Polymers 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 239000012785 packaging film Substances 0.000 claims description 41
- 229920006280 packaging film Polymers 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 238000007789 sealing Methods 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 239000006112 glass ceramic composition Substances 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229920006255 plastic film Polymers 0.000 claims description 11
- 239000002985 plastic film Substances 0.000 claims description 11
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 claims description 2
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 claims description 2
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 2
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 238000012536 packaging technology Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- 229920001721 polyimide Polymers 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 229920002379 silicone rubber Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 206010016766 flatulence Diseases 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
-
- 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
- H01M6/005—Devices for making primary cells
-
- 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
- H01M6/30—Deferred-action cells
- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
- H01M6/34—Immersion cells, e.g. sea-water cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium seawater batteries and preparation method thereof; the lithium seawater battery; cathode is protected including lithium; lithium protects cathode to be enclosed in aluminum-plastic packaging bag and be made by lithium piece, diaphragm, lithium ion solid electrolyte piece; electrolyte is impregnated in diaphragm; aluminum-plastic packaging bag is equipped with window, and for lithium ion solid electrolyte piece by packaging plastic by the window aperture seal on aluminum-plastic packaging bag, packaging plastic is high density polyethylene (HDPE) gel or high density polyethylene (HDPE)/polypropylene composite materials gel.Preparation method includes the preparation and battery assembly of the preparation for posting the lithium ion solid electrolyte piece of packaging plastic, lithium protection cathode.Lithium seawater battery of the invention has many advantages, such as that good seal performance, discharge stability are excellent, discharge time is long, energy density is high, it can be steady operation 20 days or more in simulated seawater, energy density can be more than 600Wh/kg, and preparation method has the advantages that packaging technology is simple, process is fine controllable.
Description
Technical field
The invention belongs to battery manufacturing field, it is related to a kind of lithium seawater battery and preparation method thereof.
Background technique
Lithium seawater battery is one kind using seawater as positive active material, and lithium metal is the battery system of cathode.Seawater battery
Directly as a positive electrode active material with seawater, it can reduce the self weight of power-supply system, there is longer storage life, theoretical energy
Density can be more than 2000 Wh/kg, can be information platform in Underwater resources exploration, autonomous submarine navigation device, unattended water etc.
There is the underwater equipment of high requirement to provide the high performance underwater energy battery energy density.
Since lithium piece has extremely strong reactivity with water, to fully demonstrate lithium seawater battery energy density advantage needs
Seal protection is taken to lithium piece.The lithium protected mode of current lithium seawater battery mostly uses window type sealing lamination design, wherein having
There is the solid electrolyte sheet of lithium ion conduction performance, plays a part of to construct positive and negative anodes lithium ion transport channel；In solid electrolyte
Window is constituted using polytetrafluoroethylene (PTFE) or metal material around piece, window is fixed after sealing and carries out lamination with metal lithium sheet
Encapsulation, finally constitutes the seawater battery negative pole structure with lithium defencive function.
Lithium seawater battery depend on negative pole structure lithium defencive function, and restrict cathode lithium protective value key factor it
One is solid electrolyte sheet with the sealing performance between window.Currently, there are two types of sealing means between the two: (1) physical machine
Tool formula, by way of mechanical presses, using between solid electrolyte sheet and window the deformation of rubber material reach sealing effect.
Since solid electrolyte sheet is brittle ceramic material, compressive property is poor, easily causes the broken of electrolyte sheet in extrusion process
It is broken, therefore this kind of packaged type has high requirement to the mechanical performance of electrolyte sheet and operating process；(2) chemical adhesive
Formula, this kind of mode mainly play sealing effect to the bonding effect of window and solid electrolyte sheet using polymeric binder.This
Kind mode requires polymeric binder to be intended to good adhesive property to window material and electrolyte sheet, but due to two class materials
Nature difference is larger, and currently used polymeric binder such as epoxy resin, silicon rubber etc. are difficult to meet simultaneously to window material
The requirement that is sealing adhesive of material and electrolyte.Due to the deficiency of above two sealing means, existing lithium seawater negative is easy to
Now infiltration phenomenon is so as to cause the failure of lithium seawater battery, it is difficult to embody the advantage of its high-energy density.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of good seal performance, electric discharge
Excellent in stability, the lithium seawater battery that discharge time is long, energy density is high, additionally provide that a kind of packaging technology is simple, process is smart
The preparation method of thin controllable lithium seawater battery.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of lithium seawater battery, including lithium protect cathode；The lithium protection cathode is by lithium piece, diaphragm, lithium ion solid electricity
Solution matter piece, which is enclosed in aluminum-plastic packaging bag, to be made, and is impregnated with electrolyte in the diaphragm；The aluminum-plastic packaging bag is equipped with window；Institute
It states lithium ion solid electrolyte piece and passes through packaging plastic for the window aperture seal on the aluminum-plastic packaging bag；The packaging plastic is high density
Polyethylene gel or high density polyethylene (HDPE)/polypropylene composite materials gel.
In above-mentioned lithium seawater battery, it is preferred that in the aluminum-plastic packaging bag, the lithium ion solid electrolyte piece, institute
It states diaphragm and the lithium piece is arranged with laminar, with the diaphragm between the lithium ion solid electrolyte piece and the lithium piece
It separates.
In above-mentioned lithium seawater battery, it is preferred that the aluminum-plastic packaging bag is made of aluminum-plastic packaging film；The aluminum-plastic packaging
Film is Showa aluminum plastic film CPP30, Showa aluminum plastic film CPP40, Showa aluminum plastic film CPP80；
And/or the lithium ion solid electrolyte piece is by Li1+xAlxTi2-x(PO4)3Glass-ceramic material or Li1+ xAlxGe2-x(PO4)3Glass-ceramic material is made, wherein 0.1≤x≤0.6；
And/or the diaphragm is MIcroporous polyolefin film；
And/or the electrolyte is the composite solution of lithium salts and organic solvent；The concentration of lithium salts is in the electrolyte
0.5mol/L~1.2mol/L；
And/or the high density polyethylene (HDPE)/polypropylene composite materials gel is gathered by high density polyethylene (HDPE) gel and high density
Propylene gel composition, using the high density poly propylene gel as intermediate structure supporting layer, with the high density polyethylene (HDPE) pole
Ear glue is that adhesive layer is set to intermediate structure supporting layer two sides composition three-layer sandwich structure；The high density polyethylene (HDPE) gel
Density be 0.94 g/cm3~0.98 g/cm3；The density of the high density poly propylene gel is 0.90 g/cm3~0.93
g/cm3。
In above-mentioned lithium seawater battery, it is preferred that the lithium ion solid electrolyte piece is Li1.5Al0.5Ge1.5(PO4)3Glass
Glass-ceramic material or Li1.3Al0.3Ti1.7(PO4)3Glass-ceramic material；Thickness≤40 μm of the diaphragm；The lithium salts is
LiClO4、LiPF6One or both of；The organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid
One of diethylester is a variety of.
In above-mentioned lithium seawater battery, it is preferred that the lithium seawater battery further includes seawater anode；The seawater is just extremely
Nickel foam；Thickness≤1mm of the nickel foam；The density of the nickel foam is 350 g/m2~400 g/m2。
As a general technical idea, the present invention also provides a kind of preparation method of above-mentioned lithium seawater battery, packets
Include following steps:
S1, packaging plastic and lithium ion solid electrolyte piece are subjected to thermal-adhering, obtain the lithium ion solid for posting packaging plastic
Electrolyte sheet；
S2, aluminum-plastic packaging film aperture is formed in window, with step S1 to the lithium ion solid electrolyte piece for posting packaging plastic
Fitting is sequentially placed into lithium ion solid electrolyte piece by the window aperture seal on aluminum-plastic packaging film, by packaging plastic by hot pressing
Diaphragm, lithium piece, the lithium ion solid electrolyte piece, diaphragm and lithium piece are arranged with laminar, be added electrolyte, infiltration every
Aluminum-plastic packaging bag is made in the doubling of aluminum-plastic packaging film, edge sealing by film, and Vacuum Package obtains lithium protection cathode；
The preparation of S3, completion to lithium seawater battery.
In above-mentioned preparation method, it is preferred that in the step S1, the temperature of the thermal-adhering is 160 DEG C~180 DEG C；
The time of the thermal-adhering is the min of 10 min~20.
In above-mentioned preparation method, it is preferred that in the step S2, the temperature of the hot pressing is 180 DEG C~200 DEG C；Institute
The pressure for stating hot pressing is the kPa of 1.3 kPa~3.0；The time of the hot pressing is the min of 5 min~10.
In above-mentioned preparation method, it is preferred that in the step S2, the additional amount of the electrolyte is institute every square centimeter
It states and the electrolyte 0.05g~0.2g is added in diaphragm.
In above-mentioned preparation method, it is preferred that further include the pretreatment to diaphragm and electrolyte in the step S2: will be every
Film dries 4h~12h in an inert atmosphere；Electrolyte is dried into 4h~12h in an inert atmosphere；The electrolyte it is dried
It further include the addition 4A molecular sieve into the electrolyte in journey, the volume of the 4A molecular sieve is the 1/10~1/ of electrolyte volume
8；The inert atmosphere is argon gas or nitrogen, and purity is 99.99%~99.999%；The following steps are included: it will in the step S3
Lithium protection cathode window side in step S2 is fixed with seawater anode
In preparation method of the invention, in the step S1, the packaging plastic is the tab that width is the mm of 2.5mm~4
Glue；In the step S2, the size of the window on the aluminum-plastic packaging film is relative to lithium ion solid electrolyte piece
Size is inwardly indented the mm of 2.5 mm~4；The size of the diaphragm is the ruler relative to lithium ion solid electrolyte piece
Very little size increases the mm of 3 mm~5 outward；The size of the lithium piece is identical as the lithium ion solid electrolyte piece.
In the present invention, the shape of lithium ion solid electrolyte piece is not limited only to rectangle, is also possible to triangle, pentagon etc.
The shape of polygon or round, i.e., lithium seawater battery of the present invention is also not limited to rectangle, and it is more to be also possible to triangle, pentagon etc.
Side shape or circle.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention provides a kind of lithium seawater battery, including lithium protects cathode, wherein lithium protection cathode by lithium piece, every
Film, lithium ion solid electrolyte piece are enclosed in aluminum-plastic packaging bag and are made, and electrolyte are impregnated in diaphragm, aluminum-plastic packaging bag is equipped with
Window, for lithium ion solid electrolyte piece by packaging plastic by the window aperture seal on aluminum-plastic packaging bag, packaging plastic is high-density polyethylene
Alkene gel or high density polyethylene (HDPE)/polypropylene composite materials gel.In the present invention, with high density polyethylene (HDPE) gel, high density
The compound gel of polyethylene/polypropylene is packaging plastic, is effectively realized on lithium ion solid electrolyte piece and aluminum-plastic packaging bag
Excellent sealing between window.Above-mentioned gel and aluminum-plastic packaging bag inner layer material (such as polyethylene, polypropylene) structural property one
It causes, there is good compatibility, thawing mixing can be reached under identical heating temperature, to realize abundant fitting between the two
Sealing, and under the fieWtiiltiie of above-mentioned gel, lithium ion solid electrolyte piece can keep structural property to stablize, and not heated
It influences, and gel can then be penetrated into filling lithium ion solid electrolyte piece surface pore by fusing and be reached and lithium ion solid electricity
The complete fitting and sealing for solving matter piece, overcome the binders such as epoxy resin, silicon rubber because that can not meet simultaneously to aluminum-plastic packaging
Bag and lithium ion solid electrolyte piece surface, which are fully sealed caused by requirement, protects cathode leakage problem.Relative to low density polyethylene
Alkene material, high density polyethylene (HDPE) that the present invention uses, high density polyethylene (HDPE)/polypropylene composite materials gel during heating will not
Appearance situations such as curling deformation, avoids during fitting because of interface hole caused by heat distortion；Adhesive tape itself is highly dense simultaneously
The characteristics of spending, which makes its own structure also, has higher consistency degree, can the more efficient hole for preventing water from passing through adhesive tape itself
It penetrates into inside protection cathode.As it can be seen that lithium seawater battery of the invention has preferable sealing performance.
2, make in invention using high density polyethylene (HDPE) gel, high density polyethylene (HDPE)/polypropylene composite materials gel as packaging plastic
Lithium protects cathode to have preferable sealing performance, can effectively prevent the appearance of infiltration phenomenon to avoid lithium seawater battery from losing
Effect, this enables protects the lithium seawater battery of cathode to fully demonstrate the advantage of high-energy density comprising the lithium.Lithium of the invention
Seawater battery has excellent discharge stability, and discharge time can be more than 20 days, and energy density can be more than 600 Wh/kg.
3, the present invention also provides a kind of preparation methods of lithium seawater battery, in the way of thermal-adhering by packaging plastic and lithium from
Sub- solid electrolyte sheet fitting, then makes lithium ion solid electrolyte piece pass through packaging plastic for aluminum-plastic packaging bag using hot pressing mode
On window aperture seal, the encapsulation of existing physical mechanical and sealing means based on polymeric binder can be replaced with upper type,
The sealing effect that lithium protection cathode in lithium seawater battery can significantly be improved, when extending the work of lithium seawater battery in water
Between, facilitate the advantage for embodying seawater battery high-energy density.Preparation method of the present invention is simple with packaging technology, process is fine
The advantages that controllable, can be widely used to promote in equipment under water.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the structural schematic diagram of lithium seawater battery in Example 1 and Example 2 of the present invention.
Fig. 2 is Li employed in the embodiment of the present invention 11.5Al0.5Ge1.5(PO4)3The SEM of glass-ceramic material schemes.
Fig. 3 is discharge curve of the 1Ah lithium seawater battery of the preparation of the embodiment of the present invention 1 in simulated seawater, wherein putting
Electric current density is 0.2 mA/cm2。
Fig. 4 is the pictorial diagram of the 6Ah lithium seawater battery prepared in the embodiment of the present invention 2.
Fig. 5 is discharge curve of the 6Ah lithium seawater battery of the preparation of the embodiment of the present invention 2 in simulated seawater, wherein putting
Electric current density is 0.5 mA/cm2。
Fig. 6 is discharge curve of the 6Ah lithium seawater battery of the preparation of the embodiment of the present invention 2 in simulated seawater, wherein putting
Electric current density is 0.1 mA/cm2。
Fig. 7 is the pictorial diagram after 6Ah lithium seawater battery electric discharge prepared by the embodiment of the present invention 2, wherein discharge current
Density is 0.1 mA/cm2。
Fig. 8 is the pictorial diagram after 1Ah lithium seawater battery electric discharge prepared by comparative example 1, and wherein discharge current density is
0.2 mA/cm2。
Fig. 9 is the pictorial diagram after 1Ah lithium seawater battery electric discharge prepared by comparative example 2, and wherein discharge current density is
0.2 mA/cm2。
Marginal data:
1, lithium protects cathode；2, tab；21, positive pole ear；22, negative lug；3, packaging plastic；4, aluminum-plastic packaging bag；5,
Lithium ion solid electrolyte piece；6, diaphragm；7, lithium piece；8, seawater anode.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.The experiment side of actual conditions is not specified in embodiment
Method according to conventional methods and conditions, or is selected according to product manual.
Embodiment
A kind of lithium seawater battery of the invention, the lithium seawater battery be it is a kind of based on high density polyethylene (HDPE) gel, it is highly dense
The high-energy density lithium seawater battery of the compound gel of polyethylene/polypropylene is spent, including seawater anode 8 and lithium protect cathode 1.Its
In, lithium protection cathode 1 is enclosed in aluminum-plastic packaging bag 4 and is made by lithium piece 7, diaphragm 6, lithium ion solid electrolyte piece 5, in diaphragm 6
It is impregnated with electrolyte, aluminum-plastic packaging bag 4 is equipped with window, and lithium ion solid electrolyte piece 5 passes through packaging plastic 3 for aluminum-plastic packaging bag
Window aperture seal on 4, packaging plastic 3 are high density polyethylene (HDPE) gel or high density polyethylene (HDPE)/polypropylene composite materials gel, plastic-aluminum
Lithium ion solid electrolyte piece 5, diaphragm 6 and lithium piece 7 are arranged in packaging bag 4 with laminar, lithium ion solid electrolyte piece 5 with
It is separated between lithium piece 7 with diaphragm 6.Seawater anode 8 is fixed on lithium protection 1 window side of cathode, and seawater anode 8 is nickel foam,
Thickness is no more than 1mm, and density is 350 g/m2~400 g/m2。
Embodiment 1
A kind of lithium seawater battery of the invention, as shown in Figure 1, the lithium seawater battery includes that seawater anode 8 and lithium protection are negative
Pole 1.Lithium protection cathode 1 is enclosed in aluminum-plastic packaging bag 4 and is made by lithium piece 7, diaphragm 6, lithium ion solid electrolyte piece 5, diaphragm 6
In be impregnated with electrolyte, aluminum-plastic packaging bag 4 is equipped with window, and lithium ion solid electrolyte piece 5 is by packaging plastic 3 by aluminum-plastic packaging
Window aperture seal on bag 4, packaging plastic 3 are high density polyethylene (HDPE) gel, and density is 0.976 g/cm3。
In the present embodiment, in the aluminum-plastic packaging bag 4, lithium ion solid electrolyte piece 5, diaphragm 6 and lithium piece 7 are with laminar
Arrangement, is separated between lithium ion solid electrolyte piece 5 and lithium piece 7 with diaphragm 6.
In the present embodiment, aluminum-plastic packaging bag 4 is made of aluminum-plastic packaging film, and wherein aluminum-plastic packaging film is Showa aluminum plastic film
CPP40(is Japanese Showa CPP40 type electrician plastic-aluminum packaging film), the film is by being coated with the polyimide film and polyethylene structure of aluminium layer
At wherein inner layer material is polyethylene.
In the present embodiment, lithium ion solid electrolyte piece 5 is by Li1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made；Every
Film 6 is MIcroporous polyolefin film, with a thickness of 20 μm；Electrolyte is LiPF6With ethylene carbonate, dimethyl carbonate it is compound molten
Liquid, wherein ethylene carbonate and organic solvent of the dimethyl carbonate as electrolyte, the volume ratio of the two are 1: 1；In electrolyte
LiPF6Concentration be 1 mol/L.
In the present embodiment, seawater anode 8 is fixed on lithium protection 1 window side of cathode.Seawater anode 8 is nickel foam, thickness
For 1 mm, density is 380 g/m2。
In the present embodiment, seawater anode 8 is equipped with positive pole ear 21, positioned at outside (the i.e. seawater anode 8 of seawater anode 8
The side contacted with external environment), positive pole ear 21 is nickel tab.Negative lug 22 on lithium protection cathode 1 is fixed on lithium piece 7
The surface of side is not contacted with diaphragm 6, negative lug 22 is nickel tab.
A kind of preparation method of lithium seawater battery in above-mentioned the present embodiment, comprising the following steps:
(1) pretreatment of raw material:
MIcroporous polyolefin film with a thickness of 20 μm is put into (argon gas or nitrogen, purity are full of 99.999% argon gas
99.99%~99.999%) dry 8 h in glove box.
Electrolyte is put into the hand full of 99.999% argon gas (argon gas or nitrogen, purity are 99.99%~99.999%)
Dry 8 h in casing, wherein electrolyte LiPF6With the composite solution of ethylene carbonate, dimethyl carbonate, ethylene carbonate
Organic solvent with dimethyl carbonate as electrolyte, the volume ratio of the two are 1: 1；LiPF in electrolyte6Concentration be 1
mol/L.It further include the addition 4A molecular sieve into electrolyte in the drying process of electrolyte, further to remove in electrolyte
Moisture, wherein the volume of 4A molecular sieve is the 1/10 of electrolyte volume.
(2) packaging plastic is cut:
Take commercially available Li1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made having a size of the cm(long of 4.1 cm × 4.1 × wide)
Lithium ion solid electrolyte piece 5, wherein lithium ion solid electrolyte piece 5 with a thickness of 300 μm.
It, will be with a thickness of 100 μm of high density polyethylene (HDPE) pole according to the length and width dimensions of above-mentioned lithium ion solid electrolyte piece 5
It is the cm(long of 4.1 cm × 0.3 × wide that ear glue, which is cut into length and width) adhesive tape.
(3) thermal-adhering of packaging plastic 3 and lithium ion solid electrolyte piece 5:
The high density polyethylene (HDPE) gel that length × width in step (2) is the cm of 4.1 cm × 0.3 is affixed on to the lithium of step (2)
On ion solid electrolyte sheet 5, with 5 perimeter alignment of lithium ion solid electrolyte piece, it is put in 160 DEG C of baking oven and heats 10
Min, glue to be packaged take out after sufficiently melting no obvious bubble, obtain the lithium ion solid electrolyte piece for posting packaging plastic, standby
With.
(4) lithium protection cathode 1 is prepared:
(4.1) according to the length and width dimensions of lithium ion solid electrolyte piece 5 in step (2) to the plastic-aluminum envelope with a thickness of 100 μm
It fills film (Japanese Showa CPP40 type electrician plastic-aluminum packaging film) and carries out aperture, form window, bore size is the cm of 3.5 cm × 3.5
(long × wide) obtains the aluminum-plastic packaging film equipped with window, spare.
Metal lithium bands with a thickness of 500 μm are cut into 4.1 cm(long of cm × 4.1 × wide) lithium piece 7, utilize machinery
Negative lug 22 is compressed with lithium piece 7 and is fixed with commercial polyimide high temperature gummed tape by rolling mode, obtains the lithium for posting tab
Piece, it is spare.
MIcroporous polyolefin film after pretreatment in step (1) is cut to the cm(long of 5 cm × 5 × wide) it is rectangular thin
Film obtains diaphragm 6, spare.
(4.2) window will be equipped in the lithium ion solid electrolyte piece and step (4.1) that post packaging plastic in step (3)
The fitting of aluminum-plastic packaging film, the side for making lithium ion solid electrolyte piece 5 post packaging plastic and the interior strata second in aluminum-plastic packaging film
The fitting of alkene material, and be aligned packaging plastic with window, be put in 180 DEG C of Heated Copper plate surface and apply the pressure of 1.5 kPa, heat
5 min are pressed, make lithium ion solid electrolyte piece 5 by packaging plastic by the window aperture seal on aluminum-plastic packaging film, then in indifferent gas
Under atmosphere (argon gas or nitrogen, purity are 99.99%~99.999%), the diaphragm 6 in step (4.1) is placed in lithium ion solid
The other side of electrolyte sheet 5 is fixed after alignment with commercial polyimide high temperature gummed tape, is placed into step (4.1) and is posted tab
Lithium piece, the side for not posting tab in lithium piece 7 is bonded with diaphragm 6, makes lithium ion solid electrolyte piece 5, diaphragm 6, post
The lithium piece of tab is arranged with laminar, electrolyte infiltration diaphragm 6 after pretreatment in 2.5g step (1) is taken, then by aluminium
The doubling of packaged by plastic film, edge sealing, are made aluminum-plastic packaging bag, and last Vacuum Package obtains lithium protection cathode 1.Plastic-aluminum seals in the present invention
Fill the edge sealing of film, Vacuum Package is operated according to the industry standard of this field.
(5) battery assembly:
(5.1) cm(long of 4.1 cm × 4.1 × wide will be cut to a thickness of the nickel foam of 1 mm) square piece, by positive pole
The perimeter alignment of ear 21 and nickel foam square piece, is welded and fixed, and obtains the seawater anode for posting tab.
(5.2) the lithium protection cathode window side in step (4) is bonded with the side that seawater anode 8 does not post tab,
Seawater anode 8 protects the window of cathode 1 to just with lithium, is fixed with commercial polyimide high temperature gummed tape, completes whole preparation process,
Obtain lithium seawater battery.
The lithium seawater battery of the high-energy density of embodiment 1 is characterized:
Fig. 2 is Li used by the embodiment of the present invention 11.5Al0.5Ge1.5(PO4)3The SEM of glass-ceramic material schemes.By Fig. 2
It is found that the electrolyte has fine and close microstructure, it can effectively prevent penetration of sea water to inside battery, battery is avoided to lose
Effect.Fig. 3 is discharge curve of the 1Ah lithium seawater battery of the preparation of the embodiment of the present invention 1 in simulated seawater, wherein discharge current
Density is 0.2 mA/cm2.From the figure 3, it may be seen that with 0.2 mA/cm2After current density electric discharge, the energy density of battery is 329 Wh/
Kg, discharge time reach 202 hours.
Embodiment 2
A kind of lithium seawater battery of the invention, as shown in Figure 1, the lithium seawater battery includes that seawater anode 8 and lithium protection are negative
Pole 1.Lithium protection cathode 1 is enclosed in aluminum-plastic packaging bag 4 and is made by lithium piece 7, diaphragm 6, lithium ion solid electrolyte piece 5, diaphragm 6
In be impregnated with electrolyte, aluminum-plastic packaging bag 4 is equipped with window, and lithium ion solid electrolyte piece 5 is by packaging plastic 3 by aluminum-plastic packaging
Window aperture seal on bag 4, packaging plastic 3 are high density polyethylene (HDPE)/polypropylene composite materials gel, medium high density polyethylene/poly- third
The compound gel of alkene is made of high density polyethylene (HDPE) gel and high density poly propylene gel, with high density poly propylene gel
For intermediate structure supporting layer, intermediate structure supporting layer two sides are set to as adhesive layer using high density polyethylene (HDPE) gel and are constituted three layers of folder
Core structure, the density of high density polyethylene (HDPE) gel are 0.976 g/cm3, the density of high density poly propylene gel is 0.92
g/cm3。
In the present embodiment, in the aluminum-plastic packaging bag 4, lithium ion solid electrolyte piece 5, diaphragm 6 and lithium piece 7 are with laminar
Arrangement, is separated between lithium ion solid electrolyte piece 5 and lithium piece 7 with diaphragm 6.
In the present embodiment, aluminum-plastic packaging bag 4 is made of aluminum-plastic packaging film, and wherein aluminum-plastic packaging film is Showa aluminum plastic film
CPP40(is Japanese Showa CPP40 type electrician plastic-aluminum packaging film), the film is by being coated with the polyimide film and polyethylene structure of aluminium layer
At wherein inner layer material is polyethylene.
In the present embodiment, lithium ion solid electrolyte piece 5 is by Li1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made；Every
Film 6 is MIcroporous polyolefin film, with a thickness of 40 μm；Electrolyte is LiPF6With ethylene carbonate, dimethyl carbonate it is compound molten
Liquid, wherein ethylene carbonate and organic solvent of the dimethyl carbonate as electrolyte, the volume ratio of the two are 1: 1；In electrolyte
LiPF6Concentration be 1 mol/L.
In the present embodiment, seawater anode 8 is fixed on lithium protection 1 window side of cathode.Seawater anode 8 is nickel foam, thickness
For 1 mm, density is 380 g/m2。
In the present embodiment, seawater anode 8 is equipped with positive pole ear 21, positioned at outside (the i.e. seawater anode 8 of seawater anode 8
The side contacted with external environment), positive pole ear 21 is nickel tab.Negative lug 22 on lithium protection cathode 1 is fixed on lithium piece 7
The surface of side is not contacted with diaphragm 6, negative lug 22 is nickel tab.
A kind of preparation method of lithium seawater battery in above-mentioned the present embodiment, comprising the following steps:
(1) pretreatment of raw material:
MIcroporous polyolefin film with a thickness of 40 μm is put into and is filled with 99.999% argon gas (argon gas or nitrogen, purity
Be 99.99%~99.999%) glove box in dry 8 h.
Electrolyte is put into and is filled with 99.999% argon gas (argon gas or nitrogen, purity are 99.99%~99.999%)
Dry 8 h in glove box, wherein electrolyte LiPF6With the composite solution of ethylene carbonate, dimethyl carbonate, ethylene carbonate
The volume ratio of ester and dimethyl carbonate is 1: 1, LiPF in electrolyte6Concentration be 1 mol/L.In the drying process of electrolyte
It further include the addition 4A molecular sieve into electrolyte, further to remove the moisture in electrolyte, wherein the volume of 4A molecular sieve is
The 1/10 of electrolyte volume.
(2) packaging plastic is cut:
Take commercially available Li1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made having a size of the cm(long of 6.1 cm × 6.1 × wide)
Lithium ion solid electrolyte piece 5, wherein lithium ion solid electrolyte piece 5 with a thickness of 300 μm.
It, will be with a thickness of 100 μm of high density polyethylene (HDPE)/poly- according to the length and width dimensions of above-mentioned lithium ion solid electrolyte piece 5
It is the cm(long of 6.1 cm × 0.3 × wide that the compound gel of propylene, which is cut into length and width) adhesive tape.
(3) thermal-adhering of packaging plastic 3 and lithium ion solid electrolyte piece 5:
High density polyethylene (HDPE)/polypropylene composite materials gel that length × width in step (2) is the cm of 6.1 cm × 0.3 is affixed on
On the lithium ion solid electrolyte piece 5 of step (2), with 5 perimeter alignment of lithium ion solid electrolyte piece, it is put in 180 DEG C of baking oven
20 min of middle heating, glue to be packaged take out after sufficiently melting no obvious bubble, obtain the lithium ion solid electricity for posting packaging plastic
Matter piece is solved, it is spare.
(4) lithium protection cathode 1 is prepared:
(4.1) according to the length and width dimensions of lithium ion solid electrolyte piece 5 in step (2) to the plastic-aluminum envelope with a thickness of 100 μm
It fills film (Japanese Showa CPP40 type electrician plastic-aluminum packaging film) and carries out aperture, form window, bore size is 5.5 cm × 5.5
Cm(long × wide), the aluminum-plastic packaging film equipped with window is obtained, it is spare.
Metal lithium bands with a thickness of 1000 μm are cut into 6.1 cm(long of cm × 6.1 × wide) lithium piece 7, utilize machinery
Negative lug 22 is compressed with lithium piece 7 and is fixed with commercial polyimide high temperature gummed tape by rolling mode, obtains the lithium for posting tab
Piece, it is spare.
MIcroporous polyolefin film after pretreatment in step (1) is cut to the cm(long of 7 cm × 7 × wide) it is rectangular thin
Film obtains diaphragm 6, spare.
(4.2) window will be equipped in the lithium ion solid electrolyte piece and step (4.1) that post packaging plastic in step (3)
The fitting of aluminum-plastic packaging film, the side for making lithium ion solid electrolyte piece 5 post packaging plastic and the interior strata second in aluminum-plastic packaging film
The fitting of alkene material, and be aligned packaging plastic with window, be put in 200 DEG C of Heated Copper plate surface and apply the pressure of 2.8 kPa, heat
5 min are pressed, make lithium ion solid electrolyte piece 5 by packaging plastic by the window aperture seal on aluminum-plastic packaging film, then in indifferent gas
Under atmosphere (argon gas or nitrogen, purity are 99.99%~99.999%), the diaphragm 6 in step (4.1) is placed in lithium ion solid
The other side of electrolyte sheet 5 is fixed after alignment with commercial polyimide high temperature gummed tape, is placed into step (4.1) and is posted tab
Lithium piece, the side for not posting tab in lithium piece 7 is bonded with diaphragm 6, makes lithium ion solid electrolyte piece 5, diaphragm 6, post
The lithium piece of tab is arranged with laminar, electrolyte infiltration diaphragm 6 after pretreatment in 4.9 g steps (1) is taken, then by aluminium
The doubling of packaged by plastic film, edge sealing, are made aluminum-plastic packaging bag, most obtain lithium protection cathode 1 through Vacuum Package afterwards.
(5) battery assembly:
(5.1) cm(long of 6.1 cm × 6.1 × wide will be cut to a thickness of the nickel foam of 1 mm) square piece, by positive pole
The perimeter alignment of ear 21 and nickel foam square piece, is welded and fixed, and obtains the seawater anode for posting tab.
(5.2) the lithium protection cathode window side in step (4) is bonded with the side that seawater anode 8 does not post tab,
Seawater anode 8 protects the window of cathode 1 to just with lithium, is adjacent to fixation with commercial polyimide high temperature gummed tape, completes entire preparation
Process obtains lithium seawater battery.
The lithium seawater battery of the high-energy density of embodiment 2 is characterized:
Fig. 4 is the pictorial diagram of 6Ah lithium seawater battery in the embodiment of the present invention 2.Fig. 5 is 6Ah prepared by the embodiment of the present invention 2
Discharge curve of the lithium seawater battery in simulated seawater, wherein discharge current density is 0.5 mA/cm2.As shown in Figure 5, with
0.5 mA/cm2After current density electric discharge, the energy density of battery is 658 Wh/kg, and discharge time reaches 355 hours.For test
The working performance when sealing performance of entire battery and in the seawater long, Fig. 6 is the 6Ah lithium seawater of the preparation of the embodiment of the present invention 2
Discharge curve of the battery in simulated seawater, wherein discharge current density is 0.1 mA/cm2.It will be appreciated from fig. 6 that using 0.1
mA/cm2When current density carries out long-time discharge test, discharge time is more than 20 days, embodies excellent sealing structure performance
And discharge stability.Fig. 7 is the pictorial diagram after 6Ah lithium seawater battery electric discharge prepared by the embodiment of the present invention 2, wherein discharging
Current density is 0.1 mA/cm2.In conjunction with Fig. 4,7 it is found that in 0.1mA/cm2Current density under, discharge time is more than 20 days, not
There is flatulence phenomenon, this illustrates that lithium seawater battery of the invention has preferable sealing performance, can effectively prevent infiltration phenomenon
Appearance to avoid lithium seawater battery fail so that lithium seawater battery can fully demonstrate the advantage of high-energy density.
It can be seen that lithium seawater battery of the invention has preferable sealing performance and excellent discharge stability, discharge time can
More than 20 days, energy density can be more than 600 Wh/kg.
Comparative example 1
A kind of preparation method of lithium seawater battery, using silicon rubber to lithium ion solid electrolyte piece and aluminum-plastic packaging film into
Row sealing, comprising the following steps:
(1) pretreatment of raw material:
To be put into a thickness of 20 μm of MIcroporous polyolefin films, electrolyte be filled with 99.999% argon gas (argon gas or nitrogen,
Purity is 99.99%~99.999%) glove box in dry 8 h, wherein electrolyte LiPF6With ethylene carbonate, carbonic acid two
The volume ratio of the composite solution of methyl esters, ethylene carbonate and dimethyl carbonate is 1: 1, LiPF in electrolyte6Concentration be 1
mol/L.It further include the addition 4A molecular sieve into electrolyte in the drying process of electrolyte, further to remove in electrolyte
Moisture, wherein the volume of 4A molecular sieve is the 1/10 of electrolyte volume.
(2) lithium protection cathode encapsulation:
(2.1) commercially available Li is taken1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made having a size of the cm of 4.1 cm × 4.1 ×
300 μm (length × width × height) of lithium ion solid electrolyte piece, with a thickness of 300 μm.
It is opened according to the length and width dimensions of above-mentioned lithium ion solid electrolyte piece with a thickness of 100 μm of aluminum-plastic packaging film
Hole, forms window, and bore size is the cm(long of 3.5 cm × 3.5 × wide), the aluminum-plastic packaging film for being equipped with window is obtained, it is spare.
Metal lithium bands with a thickness of 500 μm are cut into 4.1 cm(long of cm × 4.1 × wide) lithium piece, utilize mechanical rolling
Negative lug (nickel tab) is compressed with lithium piece and is posted with commercial polyimide high temperature gummed tape by pressure mode, obtains posting tab
Lithium piece, for use.
Polyolefin micropore barrier diaphragm after pretreatment in step (1) is cut to the cm(long of 5 cm × 5 × wide) it is rectangular thin
Film obtains diaphragm, spare.
(2.2) silicon rubber is applied to the lithium ion solid electrolyte piece surface in step (2.1), it is close that width is smeared in control
Approximately equal to 3 mm.Lithium ion solid electrolyte piece is coated in the side and step (2.1) of silicon rubber after smearing and is equipped with window
Aluminum-plastic packaging film fitting, be aligned lithium ion solid electrolyte piece and the window of aluminum-plastic packaging film, application 3.0 kPa pressure and
24 h are stood under air at room temperature environment, keep lithium ion solid electrolyte piece by silicon rubber that the window on aluminum-plastic packaging film is close
Envelope, then under 99.999% argon atmosphere (argon gas or nitrogen, purity are 99.99%~99.999%), by step (2.1)
In diaphragm be placed in the other side of lithium ion solid electrolyte piece, fixed after alignment with commercial polyimide high temperature gummed tape, then put
Enter the lithium piece for posting tab in step (2.1), the side for not posting tab in lithium piece is bonded with diaphragm, keeps lithium ion solid electric
Solution matter piece, diaphragm, the lithium piece for posting tab are arranged with laminar, take electrolyte leaching after pretreatment in 2.5g step (1)
Moisten diaphragm and aluminum-plastic packaging bag is made then by the doubling of aluminum-plastic packaging film, edge sealing, it is negative most to obtain lithium protection through Vacuum Package afterwards
Pole.
(3) battery assembly:
(3.1) cm(long of 4.1 cm × 4.1 × wide will be cut to a thickness of the nickel foam of 1 mm) square piece, welding anode
Tab (nickel tab) obtains the seawater anode for posting tab.
(3.2) the lithium protection cathode window side in step (2) is bonded with the side that seawater anode does not post tab, seawater
Anode protects the window of cathode to just with lithium, is adjacent to fixation with commercial polyimide high temperature gummed tape, completes whole preparation process, obtain
To lithium seawater battery.
Discharge test is carried out to 1Ah lithium seawater battery made from comparative example 1: in 0.2 mA/cm2Current density under, put
The electric time, which is no more than, occurs obvious flatulence phenomenon (as shown in Figure 8) for 20 hours, and battery discharge reaches blanking voltage termination.Fig. 8
Pictorial diagram after the 1Ah lithium seawater battery electric discharge prepared for comparative example 1, wherein discharge current density is 0.2 mA/cm2。
Comparative example 2
A kind of preparation method of lithium seawater battery, using epoxy resin to lithium ion solid electrolyte piece and aluminum-plastic packaging film
It is sealed, comprising the following steps:
(1) pretreatment of raw material:
To be put into a thickness of 20 μm of MIcroporous polyolefin films, electrolyte be filled with 99.999% argon gas (argon gas or nitrogen,
Purity is 99.99%~99.999%) glove box in dry 8 h, wherein electrolyte LiPF6With ethylene carbonate, carbonic acid two
The volume ratio of the composite solution of methyl esters, ethylene carbonate and dimethyl carbonate is 1: 1, LiPF in electrolyte6Concentration be 1
mol/L.It further include the addition 4A molecular sieve into electrolyte in the drying process of electrolyte, further to remove in electrolyte
Moisture, wherein the volume of 4A molecular sieve is the 1/10 of electrolyte volume.
(2) lithium protection cathode encapsulation:
(2.1) commercially available Li is taken1.5Al0.5Ge1.5(PO4)3Glass-ceramic material is made having a size of the cm(long of 4.1 cm × 4.1
× it is wide) lithium ion solid electrolyte piece, with a thickness of 30 μm.
It is opened according to the length and width dimensions of above-mentioned lithium ion solid electrolyte piece with a thickness of 100 μm of aluminum-plastic packaging film
Hole, forms window, and bore size is the cm(long of 3.5 cm × 3.5 × wide), the aluminum-plastic packaging film for being equipped with window is obtained, it is spare.
Metal lithium bands with a thickness of 500 μm are cut into 4.1 cm(long of cm × 4.1 × wide) lithium piece, utilize mechanical rolling
Negative lug (nickel tab) is compressed with lithium piece and is posted with commercial polyimide high temperature gummed tape by pressure mode, obtains posting tab
Lithium piece, for use.
Polyolefin micropore barrier diaphragm after pretreatment in step (1) is cut to the cm(long of 5 cm × 5 × wide) it is rectangular thin
Film obtains diaphragm, spare.
(2.2) epoxy resin and curing agent in mass ratio 1: 1 is applied in step (1) after evenly mixing having a size of 4.1
The lithium ion solid electrolyte piece surface of the cm of cm × 4.1, control smear width and are approximately equal to 3 mm.Lithium ion is consolidated after smearing
The side that body electrolyte sheet is coated with epoxy resin is bonded with the aluminum-plastic packaging film for being equipped with window in step (2.1), consolidates lithium ion
Body electrolyte sheet is aligned with the window of aluminum-plastic packaging film, is applied 3.0 kPa pressure and is stood 24 h under air at room temperature environment, makes
Lithium ion solid electrolyte piece passes through epoxy resin by the window aperture seal on aluminum-plastic packaging film, then in 99.999% argon atmosphere
Under, the diaphragm in step (2.1) is placed in the other side of lithium ion solid electrolyte piece, is fixed after alignment with diaphragm adhesive tape, then
It is put into the lithium piece for posting tab in step (2.1), the side for not posting tab in lithium piece is bonded with diaphragm, makes lithium ion solid
Electrolyte sheet, diaphragm, the lithium piece for posting tab are arranged with laminar, take electrolyte after pretreatment in 2.5g step (1)
It infiltrates diaphragm and aluminum-plastic packaging bag is made then by the doubling of aluminum-plastic packaging film, edge sealing, most obtain lithium protection through Vacuum Package afterwards and bear
Pole.
(3) battery assembly:
(3.1) it will be cut to the square piece of the cm of 4.1 cm × 4.1 with a thickness of the nickel foam of 1 mm, weld positive pole ear (nickel pole
Ear), obtain the seawater anode for posting tab.
(3.2) the lithium protection cathode window side in step (2) is bonded with the side that seawater anode does not post tab, seawater
Anode protects the window of cathode to just with lithium, is adjacent to fixation with commercial polyimide high temperature gummed tape, completes whole preparation process, obtain
To lithium seawater battery.
Discharge test is carried out to 1Ah lithium seawater battery made from comparative example 2: in 0.2 mA/cm2Current density under, put
The electric time is more than to occur obvious flatulence phenomenon (as shown in Figure 9) after 90 hours, and battery discharge reaches blanking voltage termination.Fig. 9 is
Pictorial diagram after 1Ah lithium seawater battery electric discharge prepared by comparative example 2, wherein discharge current density is 0.2 mA/cm2.Though
The sealing performance of right epoxy resin has relative to silicon rubber to be more obviously improved, but due in epoxy resin and aluminum-plastic packaging film
The poor compatibility of strata vinyl material, bond properties Shortcomings, the battery discharge later period, there are unsticking phenomenons, therefore when its electric discharge
Between it is still shorter, have obvious gap with 1-2 of the embodiment of the present invention.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Though
So the present invention is disclosed as above with preferred embodiment, and however, it is not intended to limit the invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from Spirit Essence of the invention and technical solution, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications or equivalent example modified to equivalent change to technical solution of the present invention.Therefore,
Anything that does not depart from the technical scheme of the invention are made to the above embodiment any simple according to the technical essence of the invention
Modification, equivalent replacement, equivalence changes and modification, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (10)
1. a kind of lithium seawater battery, which is characterized in that protect cathode including lithium；Lithium protection cathode by lithium piece, diaphragm, lithium from
Sub- solid electrolyte sheet is enclosed in aluminum-plastic packaging bag and is made, and is impregnated with electrolyte in the diaphragm；It is set on the aluminum-plastic packaging bag
There is window；The lithium ion solid electrolyte piece passes through packaging plastic for the window aperture seal on the aluminum-plastic packaging bag；The encapsulation
Glue is high density polyethylene (HDPE) gel or high density polyethylene (HDPE)/polypropylene composite materials gel；High density polyethylene (HDPE)/the polypropylene
Compound gel is made of high density polyethylene (HDPE) gel and high density poly propylene gel, with the high density poly propylene tab
Glue is intermediate structure supporting layer, is set to intermediate structure supporting layer two sides by adhesive layer of the high density polyethylene (HDPE) gel
Constitute three-layer sandwich structure；The density of the high density polyethylene (HDPE) gel is 0.94 g/cm3~0.98 g/cm3；It is described highly dense
The density for spending polypropylene gel is 0.90 g/cm3~0.93 g/cm3。
2. lithium seawater battery according to claim 1, which is characterized in that in the aluminum-plastic packaging bag, the lithium ion is solid
Body electrolyte sheet, the diaphragm and the lithium piece are arranged with laminar, the lithium ion solid electrolyte piece and the lithium piece
Between separated with the diaphragm.
3. lithium seawater battery according to claim 2, which is characterized in that the aluminum-plastic packaging bag is by aluminum-plastic packaging film system
At；The aluminum-plastic packaging film is Showa aluminum plastic film CPP30, Showa aluminum plastic film CPP40, Showa aluminum plastic film CPP80；
And/or the lithium ion solid electrolyte piece is by Li1+xAlxTi2-x(PO4)3Glass-ceramic material or Li1+xAlxGe2-x
(PO4)3Glass-ceramic material is made, wherein 0.1≤x≤0.6；
And/or the diaphragm is MIcroporous polyolefin film；
And/or the electrolyte is the composite solution of lithium salts and organic solvent；The concentration of lithium salts is in the electrolyte
0.5mol/L~1.2mol/L.
4. lithium seawater battery according to claim 3, which is characterized in that the lithium ion solid electrolyte piece by
Li1.5Al0.5Ge1.5(PO4)3Glass-ceramic material or Li1.3Al0.3Ti1.7(PO4)3Glass-ceramic material is made；The diaphragm
Thickness≤40 μm；The lithium salts is LiClO4、LiPF6One or both of；The organic solvent is ethylene carbonate, carbon
One of acid propylene ester, dimethyl carbonate, diethyl carbonate are a variety of.
5. lithium seawater battery according to any one of claims 1 to 4, which is characterized in that the lithium seawater battery also wraps
Include seawater anode；The seawater just extremely nickel foam；Thickness≤1mm of the nickel foam；The density of the nickel foam is 350
g/m2~400 g/m2。
6. a kind of preparation method such as lithium seawater battery according to any one of claims 1 to 5, which is characterized in that including with
Lower step:
S1, packaging plastic and lithium ion solid electrolyte piece are subjected to thermal-adhering, obtain the lithium ion solid electrolysis for posting packaging plastic
Matter piece；
S2, aluminum-plastic packaging film aperture is formed into window, is bonded with the lithium ion solid electrolyte piece for posting packaging plastic in step S1,
Make lithium ion solid electrolyte piece by packaging plastic by the window aperture seal on aluminum-plastic packaging film by hot pressing, be sequentially placed into diaphragm,
Lithium piece, the lithium ion solid electrolyte piece, diaphragm and lithium piece are arranged with laminar, and electrolyte is added, and diaphragm are infiltrated, by aluminium
The doubling of packaged by plastic film, edge sealing, are made aluminum-plastic packaging bag, and Vacuum Package obtains lithium protection cathode；
The preparation of S3, completion to lithium seawater battery.
7. preparation method according to claim 6, which is characterized in that in the step S1, the temperature of the thermal-adhering is
160 DEG C~180 DEG C；The time of the thermal-adhering is the min of 10 min~20.
8. preparation method according to claim 6, which is characterized in that in the step S2, the temperature of the hot pressing is 180
DEG C~200 DEG C；The pressure of the hot pressing is the kPa of 1.3 kPa~3.0；The time of the hot pressing is the min of 5 min~10.
9. the preparation method according to any one of claim 6~8, which is characterized in that in the step S2, the electrolysis
The additional amount of liquid is that the electrolyte 0.05g~0.2g is added in the diaphragm every square centimeter.
10. the preparation method according to any one of claim 6~8, which is characterized in that further include pair in the step S2
The pretreatment of diaphragm and electrolyte: diaphragm is dried into 4h~12h in an inert atmosphere；Electrolyte is dried into 4h in an inert atmosphere
~12h；It further include addition 4A molecular sieve, the body of the 4A molecular sieve into the electrolyte in the drying process of the electrolyte
Product is the 1/10~1/8 of electrolyte volume；The inert atmosphere is argon gas or nitrogen, and purity is 99.99%~99.999%；It is described
The following steps are included: the lithium protection cathode window side in step S2 is fixed with seawater anode in step S3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195949.5A CN106935743B (en) | 2017-03-29 | 2017-03-29 | Lithium seawater battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195949.5A CN106935743B (en) | 2017-03-29 | 2017-03-29 | Lithium seawater battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106935743A CN106935743A (en) | 2017-07-07 |
| CN106935743B true CN106935743B (en) | 2019-06-28 |
Family
ID=59425227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710195949.5A Active CN106935743B (en) | 2017-03-29 | 2017-03-29 | Lithium seawater battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106935743B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659455B (en) * | 2018-12-20 | 2021-04-27 | 中国人民解放军国防科技大学 | Lithium seawater battery pack and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227264A (en) * | 1991-02-14 | 1993-07-13 | Hydro-Quebec | Device for packaging a lithium battery |
| WO2007021717A2 (en) * | 2005-08-09 | 2007-02-22 | Polyplus Battery Company | Compliant seal structures for protected active metal anodes |
| JP6269761B2 (en) * | 2016-09-15 | 2018-01-31 | 油化電子株式会社 | Method for producing laminated film for battery exterior |
| CN106784422B (en) * | 2016-12-28 | 2020-02-21 | 国联汽车动力电池研究院有限责任公司 | Double-sided soft package lithium air battery capable of being rapidly packaged and preparation method thereof |
-
2017
- 2017-03-29 CN CN201710195949.5A patent/CN106935743B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106935743A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6673249B2 (en) | Manufacturing method of laminated all solid state battery | |
| CN103608948B (en) | With the dividing plate of heat-resistant insulating layer | |
| JP5448964B2 (en) | All solid-state lithium ion secondary battery | |
| CN106784993A (en) | Flexible polymer thin lithium ion battery and preparation method thereof | |
| KR102654517B1 (en) | Pouch type metal air battery | |
| CN113261151A (en) | Separator for electrochemical device, and electronic device | |
| JPWO2018016166A1 (en) | battery | |
| CN105449255A (en) | Electrochemical energy storage device | |
| CN101414670A (en) | Battery pack and method for producing the same | |
| CN110085792A (en) | A kind of novel lithium battery isolation film and the lithium ion battery containing the isolation film | |
| CN106784422A (en) | It is a kind of can fast packing two-sided Soft Roll lithium-air battery and preparation method thereof | |
| JP2005243303A (en) | Member for electrochemical element and its manufacturing method, and the electrochemical element using it | |
| WO2022001235A1 (en) | Separator for electrochemical apparatus, electrochemical apparatus, and electronic apparatus | |
| CN106935743B (en) | Lithium seawater battery and preparation method thereof | |
| JP3651609B2 (en) | Thermally activated microporous membrane and its use in batteries | |
| WO2003105258A1 (en) | Lithium based electrochemical devices having a ceramic separator glued therein by an ion conductive adhesive | |
| JP2002110252A (en) | Method of producing battery | |
| JP6335938B2 (en) | Bipolar lithium ion battery having improved hermeticity and associated manufacturing method | |
| JPH10261386A (en) | Battery case and battery | |
| CN206340623U (en) | Battery roll core, lithium battery and terminal | |
| JP4075234B2 (en) | Solid electrolyte battery and manufacturing method thereof | |
| WO2017169417A1 (en) | Lithium-ion secondary battery | |
| CN208589492U (en) | A kind of high capacity cylinder flexible packing lithium ion battery | |
| CN103400946B (en) | Special flexible packaging film for lithium-ion power battery and energy storage lithium battery and preparation method thereof | |
| CN113851792B (en) | Soft package lithium ion battery and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |