CN102800889A - Lithium-ion battery and preparation method for same - Google Patents
Lithium-ion battery and preparation method for same Download PDFInfo
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- CN102800889A CN102800889A CN2011101387287A CN201110138728A CN102800889A CN 102800889 A CN102800889 A CN 102800889A CN 2011101387287 A CN2011101387287 A CN 2011101387287A CN 201110138728 A CN201110138728 A CN 201110138728A CN 102800889 A CN102800889 A CN 102800889A
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a lithium-ion battery, comprising a shell and a pole core contained in the shell, wherein the pole core comprises a positive pole, a negative pole, and a diaphragm located between the positive pole and the negative pole; and a liquid-state electrolyte is contained in the pole core, and a gel is filled between the pole core and the shell. The invention further provides a preparation method for the lithium-ion battery, comprising the following steps of: step 1, covering a rubberized fabric on the pole core, so as to form a sealed space in the pole core; and step 2, filling the liquid-state electrolyte in the sealed space of the pole core and performing pre-charge formation at first, and then filling second solution between the shell and the pore core, and heating to initiate a polymerization reaction, so as to form a gel between the pole core and the shell; or, filling second solution between the shell and the pore core, and heating to initiate a polymerization reaction, so as to form a gel between the pole core and the shell at first, and then filling the liquid-state electrolyte in the sealed space of the pole core and performing pre-charge formation. According to the invention, a problem of the leakage of the electrolyte is overcome, and the SEI (solid electrolyte interface) film of the negative pole cannot be influenced.
Description
Technical field
The present invention relates to the battery technology field, more particularly, relate to a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery has been widely used in fields such as mobile communication, notebook computer, video camera, camera, portable instrument as the high-energy-density chemical power source; Also be the electric automobile studied energetically of various countries, the first-selected supporting power supply of space power system, become the first-selection of the alternative energy.Different according to the used electrolyte of lithium ion battery; Lithium ion battery can be divided into liquid lithium ionic cell (lithium ion battery; Abbreviate LIB as) and polymer Li-ion battery (polymer lithium ion battery abbreviates PLIB as) two big classes.The used positive and negative pole material of polymer Li-ion battery all is identical with liquid lithium ion, and the operation principle of battery is basically identical also.Their main distinction is electrolytical difference; What traditional lithium ion battery used is liquid electrolyte; Have the problem on the safety such as liquid electrolyte leakage, combustion explosion, polymer Li-ion battery then replaces with solid polymer electrolyte or gel polymer electrolyte, compares with liquid lithium ionic cell; But have advantages such as thin typeization, arbitrary shapeization, the problem on the safety such as the liquid leakage that also can not produce electrolysis.
Wherein, gel polymer electrolyte promptly has the not characteristics of flowable of solid polymer electrolyte, has the high ionic conductivity that approaches liquid electrolyte again simultaneously, is widely used in the present polymer Li-ion battery.The use of gel state electrolyte in lithium ion battery, overcome liquid lithium ion battery intrinsic leakage, potential safety hazards such as corrosion.The preparation method of the gel state electrolyte that adopts at present mainly contains two kinds: a kind of Bellcore technology that is based on physics swelling principle; Another kind is based on the in-situ polymerization technology of chemical crosslinking polymerization.
The U.S. Bellcore technology initiative development physical gel/solution technique; Their technical process is for adopting Kynoar-hexafluoropropylene copolymer (PVDF-HFP) as the skeletal matrix material; Prepare porous membrane through abstracting method; Through physical adsorption process, electrolyte gets in the hole of PVDF-HFP barrier film.In whole technical process, the production of polymer dielectric does not relate to courses of reaction such as chemical polymerization.Yet the polymer dielectric of Bellcore technical matters preparation is the solid-liquid two-phase system, does not have chemical b ` between copolymer and the electrolyte, under receiving certain pressure or temperature two liquid phases in mutually exist flow out maybe, have potential safety hazard.
In-situ polymerization technology is in the system that contains unsaturated monomer, initator and electrolyte, to pass through method trigger monomer generation chemical polymerizations such as heating or light radiation, forms gel.Adopt this method to prepare electrolyte and overcome the shortcoming that Bellcore technology exists, this technology is simple relatively in addition, receives widely paying close attention to.
For example: application number is that CN200410026814.9 discloses a kind of polymer electrolyte lithium-ion battery, and it mainly is made up of positive and negative electrode composite component, barrier film composite component and four kinds of composite components of external packing composite component between the positive and negative electrode composite component; Wherein diaphragm element is with the barrier film of the knitmesh shape fibre structure skeleton as composite component, adds the amalgam that the colloidal state polymer electrolyte is formed, and it is characterized in that: polymer dielectric alternately is present in the surface and micropore of said barrier film with continuous state; Described continuous state forms after replacing that electrolytic polymer grows the two and three dimensions polymer network by monomer and initator generation thermopolymer chemical reaction and producing chemical action with electrolyte.
The electrolyte that in-situ polymerization technology will contain with polymerization single polymerization monomer and initator together injects battery container, and initiated polymerization settles the formation gel at one go.Skilled in the art will recognize that; In existing lithium battery preparation technology; Adopt material with carbon element as negative pole, all have one to change into precharge process, its objective is in the carbon negative terminal surface to form a stable solid electrolyte interface (solid electrolyte interface common name SEI film).The character quality of SEI film has determined the chemical property of lithium battery, especially cycle performance.Yet; No matter in-situ polymerization technology be before changing into or changing into the back polymerization, the existing of unsaturated monomer wherein and initator (or remaining), all can worsen the formed SEI film of negative terminal surface when changing into inevitably; Influence the chemical property of battery, particularly cycle performance significantly.
Summary of the invention
The present invention is intended to solve electrolyte leakage, the poor safety performance that liquid lithium ionic cell exists in the prior art, thereby and gel state lithium ion battery exists unsaturated monomer and initator to worsen the technical problem that negative pole SEI film influences the chemical property of battery.
For this reason; The invention provides a kind of lithium ion battery, comprise housing, be contained in the pole piece in the housing, said pole piece comprises positive pole, negative pole, barrier film between both positive and negative polarity; Wherein: contain liquid electrolyte in the said pole piece, be filled with gel between said pole piece and the housing.
In lithium ion battery of the present invention; Said pole piece by positive pole, negative pole, membrane coil between positive and negative electrode around forming; Be coated with adhesive plaster on the pole piece behind the coiling and make and be formed for accommodating the seal cavity of liquid electrolyte in the pole piece, and on pole piece, leave first liquid injection port that is used to inject liquid electrolyte.
In lithium ion battery of the present invention, said first liquid injection port is located at the top of pole piece, and first liquid injection port passes adhesive plaster; Said adhesive plaster is coated on the coiling end of the pole piece behind the coiling, the bottom of pole piece and the zone of top except that first liquid injection port of pole piece.
In lithium ion battery of the present invention, said housing is provided with second liquid injection port that is used to inject second solution that forms gel, and said second liquid injection port is away from said first liquid injection port.
In lithium ion battery of the present invention, said gel is the polymer that the acrylic ester monomer polymerization of one or more unsaturated double-bonds forms.
Simultaneously, the preparation method of above-mentioned lithium ion battery is provided also, said preparation method comprises the steps: step 1, on pole piece, coats adhesive plaster, makes and forms seal cavity in the pole piece;
In the preparation method of lithium ion battery of the present invention, the temperature of said heating initiated polymerization is 60-100 ℃, and the time is 10-120min.
In the preparation method of lithium ion battery of the present invention; Said liquid electrolyte contains the lithium salts and first solvent; The concentration of lithium salts is 0.5-1.5mol/L; Wherein, said lithium salts is selected from a kind of or two or more in lithium hexafluoro phosphate, lithium perchlorate, LiBF4, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfoamido lithium, the biethyl diacid lithium borate; The carbonates solvent that said first solvent is straight chain or ring-type.
In the preparation method of lithium ion battery of the present invention; Said second solution comprises unsaturated monomer, initator and second solvent; Said unsaturated monomer is the acrylic ester monomer that contains one or more unsaturated double-bonds; Said thermal initiator is selected from a kind of or two or more in dibenzoyl peroxide, azobisisobutyronitrile, the accelerine, and the said second solvent package carbonate-containing kind solvent is or/and halo carbonates solvent; Total weight with second solution is a benchmark, and the content of said unsaturated monomer is 3wt-30wt%, and the content of said initator is 0.5wt-3wt%, and the content of second solvent is 67wt-96.5wt%.
In the preparation method of lithium ion battery of the present invention; Said second solvent also comprises organic phosphorus compound; Said organic phosphorus compound are selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributyl phosphate, tricresyl phosphate (2-chloroethyl) ester, methyl-phosphoric acid dimethyl ester, vinyl ethyl phosphonic acid ester, a kind of or two or more in the hexamethyl phosphoramide.
In the preparation method of lithium ion battery of the present invention; With positive pole, negative pole, membrane coil between positive and negative electrode around forming pole piece; Coating adhesive plaster on the pole piece behind coiling makes and forms seal cavity in the pole piece; And on pole piece, be reserved with first liquid injection port that is used to inject liquid electrolyte, in pole piece, inject liquid electrolyte through said first liquid injection port.
In the preparation method of lithium ion battery of the present invention, second liquid injection port is set on housing, said second liquid injection port is injected second solution away from said first liquid injection port through said second liquid injection port in housing.
Preparation method of the present invention fluid injection at twice; Battery changed into two processes of monomer polymerization separate; In the step that precharge changes into, in pole piece, inject first solution, adopt first solution (being liquid electrolyte) to change into; Known chemical synthesis technology according to this area forms stable SEI film in the carbon negative terminal surface, guarantees the chemical property of battery; In the step of monomer polymerization, between pole piece and housing, inject second solution, heating initiated polymerization, preparation polymer gel.Compare with existing in-situ polymerization technology; The lithium battery of the present invention's preparation has been avoided the influence of monomer and initator anticathode SEI film; Can guarantee to obtain excellent electrochemical properties, especially cycle performance is surrounded by gel because of Battery Pole Core simultaneously; Gel can absorb the liquid electrolyte that possibly flow out in the pole piece, has reduced battery leakage, burn into burning equivalent risk widely; In a word, adopt preparation method of the present invention to make lithium ion battery and not only overcome the electrolyte leakage that existing liquid lithium ionic cell exists, the problem of poor safety performance, and can not influence negative pole SEI film, guaranteed the chemical property of lithium ion battery.
Description of drawings
Fig. 1 is the sketch map of the pole piece of lithium ion battery of the present invention.
Fig. 2 is the cycle performance comparison diagram of the lithium ion battery that makes of the embodiment of the invention 1, Comparative Examples 1, Comparative Examples 2.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention is solved, below in conjunction with accompanying drawing and embodiment, the present invention is further elaborated.
Those skilled in the art will appreciate that there is the problem on the safety such as liquid electrolyte leakage, combustion explosion in the liquid lithium ionic cell that adopts liquid electrolyte.Simultaneously; The inventor finds through experiment repeatedly; Adopt existing in-situ polymerization technology to make gel polymer electrolyte, the remnants after the monomer that is added and the existence of initator or the polymerization then can influence the performance of the SEI film on the negative terminal surface significantly; This will directly cause battery performance to reduce, for example the reduction of the cycle performance of battery etc.
Inventor of the present invention has carried out further research; Battery changed into two processes of monomer polymerization separate; In the step that precharge changes into, in pole piece, inject first solution, adopt first solution (being liquid electrolyte) to change into; Known chemical synthesis technology according to this area forms stable SEI film in the carbon negative terminal surface, guarantees the chemical property of battery; In the step of monomer polymerization, between pole piece and housing, inject second solution, heating initiated polymerization, preparation polymer gel.Compare with existing in-situ polymerization technology, the lithium battery of the present invention's preparation has been avoided the influence of monomer and initator anticathode SEI film, can guarantee that lithium ion battery obtains excellent electrochemical properties, especially cycle performance; Simultaneously, because Battery Pole Core is surrounded by gel, gel can absorb the liquid electrolyte that possibly flow out in the pole piece, has reduced battery leakage, burn into burning equivalent risk widely, and security performance has raising significantly.
In view of the above, the invention provides a kind of lithium ion battery and preparation method thereof, evaded the influence of monomer and initator anticathode SEI film preferably, and had preferable security performance.Lithium ion battery provided by the invention comprises: housing, be contained in the pole piece in the housing, said pole piece comprises positive pole, negative pole, between positive and negative electrode barrier film, contain liquid electrolyte in the said pole piece, be filled with gel between said pole piece and the housing.
The pole piece structure of lithium ion battery of the present invention can be similar with existing liquid lithium ion battery, and said liquid electrolyte is contained in the barrier film.
Contain or do not contain conductible lithium ion in the said gel; Preferably, do not contain conductible lithium ion in the said gel, thereby said gel does not use as gel state electrolyte; It mainly acts on and absorbs the liquid electrolyte that possibly flow out in the pole piece, improves the security performance of lithium ion battery.
The invention provides two kinds of methods of the above-mentioned lithium ion battery of preparation, described two kinds of preparation methods change into battery with two steps of monomer polymerization and separate, and the order of these two steps can be exchanged.First kind of preparation method comprises the steps: 1, first with first solution, and promptly liquid electrolyte injects the seal cavity of pole piece, carries out precharge and changes into; 2, then second solution is injected between housing and the pole piece, the heating initiated polymerization forms gel between pole piece and housing, obtain lithium ion battery of the present invention.Second kind of preparation method comprises the steps: 1, earlier second solution injected between housing and the pole piece, and the heating initiated polymerization forms gel between pole piece and housing; 2, then with first solution, promptly liquid electrolyte injects the seal cavity of pole piece, carries out precharge and changes into, and obtains lithium ion battery of the present invention.In the present invention, preferably adopt second kind of preparation method to prepare lithium ion battery, make that the security performance of lithium ion battery is better in the process that precharge changes into.What deserves to be mentioned is; Before above-mentioned steps, also be included in and coat adhesive plaster on the pole piece; Make the step that forms seal cavity in the pole piece, the seal cavity of said pole piece makes second solution can not get in the pole piece, and the solution of winning can not spilt from pole piece under normal condition.
In the preparation method of two kinds of above-mentioned lithium ion batteries, said first solution is the electrolyte that contains lithium salts, comprises the lithium salts and first solvent, and lithium salts is dissolved in first solvent, and the concentration of lithium salts is 0.5-1.5mol/L.Wherein, described lithium salts is that the present technique field is known, can be lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), bis trifluoromethyl sulfoamido lithium (LiN (CF
3SO
2)
2), the one or more kinds of mixtures in the biethyl diacid lithium borate (LiBOB).The carbonates solvent that described first solvent is straight chain or ring-type; Preferably, said first solvent is selected from a kind of or two or more in ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), dimethoxy carbonic ester (DME), vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), the chlorocarbonic acid vinyl acetate (ClEC).
Described second solution comprises second solvent, unsaturated monomer and initator; Said unsaturated monomer and initator are dissolved in second solvent; The effect of said second solution is to form gel, and when heating, initator causes the polymerization of unsaturated monomers reaction and generates gel.Contain or do not contain lithium salts in said second solution, preferably, do not contain lithium salts in said second solution, do not participate in electrochemical process and ionic conduction; The main effect of said second solution is to form gel, is different from the gel state electrolyte in the existing gel state lithium ion battery, need not have the effect of electrolyte concurrently.
Wherein, first solvent of said second solvent and first solution can be identical also can be inequality, preferably, said second solvent and first solvent are inequality, are as the criterion with the weight of second solution, the content of second solvent is 67wt-96.5wt%.Particularly; The second solvent package carbonate-containing kind solvent is or/and halo carbonates solvent; Particularly, said second solvent is selected from a kind of or two or more in ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), dimethoxy carbonic ester (DME), vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), the chlorocarbonic acid vinyl acetate (ClEC).Further; Said second solvent also comprises organic phosphorus compound; Particularly; Said organic phosphorus compound are selected from a kind of or two or more in trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), triphenyl phosphate (TPP), tributyl phosphate (TBP), tricresyl phosphate (2-chloroethyl) ester (TCEP), methyl-phosphoric acid dimethyl ester (DMMP), vinyl ethyl phosphonic acid ester (EEP), the hexamethyl phosphoramide (TMPA); Awkward combustion of the organic phosphorus compound that contain in said second solvent or fire-retardant phosphide; After heating causes second solution polymerization formation gel, contain combustion in distress or fire-retardant phosphide in the said gel, make the security performance of lithium ion battery that raising significantly arranged.
Described unsaturated monomer is the acrylic ester monomer that contains one or more unsaturated double-bonds; Preferably, described unsaturated monomer is selected from a kind of or two or more in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethylene glycol dimethacrylate, TEG dimethylacrylate, glycol diacrylate, the polyethylene glycol dimethacrylate; Weight with second solution is as the criterion, and the content of monomer is 3wt-30wt%.
Said thermal initiator is selected from a kind of or two or more in dibenzoyl peroxide, azodiisobutyronitrile, the accelerine; Weight with second solution is as the criterion, and the content of initator is 0.5wt-3wt%.
Through heating, said thermal initiator causes the polymerization of unsaturated monomers reaction, and the temperature of said heating initiated polymerization is 60-100 ℃; Time is 10-120min; Make said second solution form gel, temperature is low excessively, and the speed of initiated polymerization is slow even can't initiated polymerization; Temperature is too high, then causes the volatilization of solvent easily, has influence on the performance of battery.
First kind of preparation method of above-mentioned lithium ion battery specifically may further comprise the steps:
Step 3, on the housing of battery, be provided for injecting second liquid injection port of second solution, second solution be injected into the housing of the battery after changing into through precharge from second liquid injection port; In this step, what deserves to be mentioned is that said second liquid injection port is located on the housing away from the position of said first liquid injection port, can be located at optional position not relative with first liquid injection port on the housing, get into pole piece to avoid second solution through first liquid injection port.As the case may be, the position of said second liquid injection port can be the optional position except that first liquid injection port.
Step 4, battery is heated to 60 ℃ to 100 ℃ initiated polymerizations, makes second solution in the housing form gel.In this step, the temperature of heating is 60-100 ℃; Temperature is low excessively, and the speed of initiated polymerization is slow even can't initiated polymerization; Temperature is too high, then causes the volatilization of solvent easily, has influence on the performance of battery, and under preferable case, the temperature of heating is 75-90 ℃; Be 10-120min heating time, and the mode of heating can be various heating means known in those skilled in the art.
Second kind of preparation method of above-mentioned lithium ion battery specifically may further comprise the steps:
Step 3, battery is heated to 60 ℃ to 100 ℃ initiated polymerizations, makes second solution in the housing form gel.In this step, the temperature of heating is 60-100 ℃; Temperature is low excessively, and the speed of initiated polymerization is slow even can't initiated polymerization; Temperature is too high, then causes the volatilization of solvent easily, has influence on the performance of battery, and under preferable case, the temperature of heating is 75-90 ℃; Be 10-120min heating time.
Step 4, in the seal cavity of the pole piece of battery, inject first solution, and the battery that will contain first solution carries out precharge and changes into from first liquid injection port; In this step, described precharge changes into the precharging technique for forming that can adopt this area general, changes in negative terminal surface through precharge and forms stable SEI film.
In through above-mentioned two kinds of preparation method's lithium ion cell prepared; Said pole piece by positive pole, negative pole, membrane coil between positive and negative electrode around forming; Be coated with adhesive plaster on the pole piece behind the coiling and make and be formed for accommodating the seal cavity of liquid electrolyte in the pole piece, and on pole piece, leave first liquid injection port that is used to inject liquid electrolyte; Said housing is provided with second liquid injection port that is used to inject second solution that forms gel, and said second liquid injection port is away from said first liquid injection port.As shown in Figure 1, preferably, said first liquid injection port 11 is located at the top of pole piece 1, and first liquid injection port 11 passes adhesive plaster 2; Said adhesive plaster 2 is coated on that the coiling of the pole piece 1 behind the coiling is terminal, the bottom of pole piece 1 and the zone of top except that first liquid injection port 11 of pole piece 1, makes the seal cavity that is formed for accommodating liquid electrolyte in the pole piece.
Inventor of the present invention studies further; Through twice fluid injection; Battery changed into two processes of monomer polymerization separate, in the step that precharge changes into, in pole piece, inject first solution (being liquid electrolyte); Known chemical synthesis technology according to this area forms stable SEI film in the carbon negative terminal surface, guarantees the chemical property of battery; In the step of monomer polymerization, between pole piece and housing, inject second solution, heating initiated polymerization, preparation polymer gel.Simultaneously; In the process of injecting second solution, through controlling the position of second liquid injection port, it is inner to avoid second solution to get into pole piece; Make it to be attached on more on the inwall of battery container and the outside of Battery Pole Core; Be between battery container and the pole piece, between the inboard of the outside of pole piece and housing, form gel behind the heated polymerizable, encase the pole piece in the housing.
Compare with existing in-situ polymerization technology, the lithium battery of the present invention's preparation has been avoided the influence of monomer and initator anticathode SEI film, can guarantee to obtain superior chemical property; Especially cycle performance; Because the pole piece of battery is surrounded by gel, gel can absorb the liquid electrolyte that possibly flow out in the pole piece, for example: when battery is inverted simultaneously; Liquid electrolyte may flow out from first liquid injection port, and the setting of gel has reduced battery leakage, burn into burning equivalent risk widely; Further, contain combustion in distress or fire-retardant phosphide in the gel, security performance has raising significantly.
The present invention does not have special restriction for the composition of positive pole, negative pole and the barrier film of lithium ion battery, can be positive pole, negative pole and the barrier film of this area any known, and for example, anodal collector can be aluminium foil, and the positive electrode active materials that applies on the aluminium foil can be LiCoO
2,LiMn
2O
4,LiFePO
4,LiNi
1/3Mn
1/3Co
1/3O
2Deng positive electrode active materials, and said negative pole can be for containing the Copper Foil of graphite.
In addition, need to prove, in the present invention, " more than ", " following " include given figure.
To combine specific embodiment that the present invention is done further detailed description below, and should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
With barrier film and positive and negative electrode material (LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; With the bottom of pole piece, the coiling end sticks on a piece of adhesive tape, and after first liquid injection port was reserved at the top of pole piece, all the other positions stuck on a piece of adhesive tape; Contain LiPF from the injection of first liquid injection port
6With first solution of EC-EMC-DEC-VC organic solvent, wherein, LiPF
6Concentration is 1mol/L, and the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5, after the ageing, battery is carried out precharge; Then from second liquid injection port; Be second solution of EC-EMC-DEC-VC mixed solvent that is injected dibenzoyl peroxide and the 90wt% of the TEG dimethylacrylate that contains 9 wt%, 1wt% on the housing with respect to pole piece by the position of adhesive plaster parcel; Wherein, the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5; 80 ℃ are heated 60min down, and heating causes second polymerisation in solution and forms gel, obtains lithium ion battery A1.
Comparative Examples 1
Comparative Examples 1 is used to explain that available technology adopting changes into the lithium ion battery of back polymerization;
Weight with total electrolyte is as the criterion; Preparation contains the electrolyte of 1M LiPF6/EC-EMC-DEC-VC mixed solvent of dibenzoyl peroxide and 90wt% of TEG dimethylacrylate, the 1wt% of 9 wt%; Wherein, the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5.With barrier film and positive and negative electrode material (for example: LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core, pole piece bottom, coiling end are stuck on a piece of adhesive tape, after first liquid injection port was reserved at the top of pole piece, all the other positions stuck on a piece of adhesive tape.Inject the electrolyte of above-mentioned preparation from first liquid injection port, after changing into, heat 60min down, cause the electrolyte polymerization and form gel, obtain lithium ion battery B1 at 80 ℃.
Comparative Examples 2
Comparative Examples 2 is used to explain the lithium ion battery that changes into after the available technology adopting polymerization;
The weight of separating liquid with total is as the criterion; Preparation contains the electrolyte of 1M LiPF6/EC-EMC-DEC-VC mixed solvent of dibenzoyl peroxide and 90wt% of TEG dimethylacrylate, the 1wt% of 9 wt%; Wherein, the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5.With barrier film and positive and negative electrode material (for example: LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core.Pole piece bottom, coiling end are stuck on a piece of adhesive tape, and after the first liquid injection port territory was reserved at the top of pole piece, all the other positions stuck on a piece of adhesive tape.Inject the electrolyte of above-mentioned preparation from first liquid injection port, heat 60min down, cause the electrolyte polymerization and form gel, carry out chemical synthesis technology then, obtain lithium ion battery B2 at 80 ℃.
Performance test
Fig. 2 is the cycle performance comparison diagram of the lithium ion battery that makes of the embodiment of the invention 1, Comparative Examples 1, Comparative Examples 2, can know that from Fig. 2 the cycle performance of the lithium ion battery that the embodiment of the invention 1 makes is better.
With barrier film and positive and negative electrode material (for example: LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; With the pole piece bottom, the coiling end sticks transparent rubberized fabric, and after the first liquid injection port territory was reserved at the top of pole piece, transparent rubberized fabric was sticked in all the other positions.Inject 1M from first liquid injection port and contain LiPF
6With first solution of EC-EMC-VC, wherein, LiPF
6Concentration be 0.6mol/L, the weight ratio of EC:EMC:VC is 3:6.5:0.5, after the ageing, battery is carried out precharge; Then from second liquid injection port; Be to be contained the methyl methacrylate monomer of 20 wt%, dibenzoyl peroxide and the EC of 79.5wt% and second solution of DMC mixed solvent of 0.5wt% with respect to pole piece by the position injection that adhesive plaster coats on the housing, wherein the weight ratio of EC:DMC is=1:1; 60 ℃ are heated 180min down, and heating causes second polymerisation in solution and forms gel, obtains lithium ion battery A2.
Embodiment 3
With barrier film and positive and negative electrode material (for example: LiMn
2O
4Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; Bottom, the coiling end of pole piece are sticked transparent rubberized fabric, and after first liquid injection port was reserved at the top of pole piece, all the other positions stuck on a piece of adhesive tape; Contain LiBF from the injection of first liquid injection port
4With first solution of EC-EMC-DEC-VC organic solvent, wherein, LiBF
4Concentration is 1mol/L, and the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5, after the ageing, battery is carried out precharge; Then from second liquid injection port; Be second solution of EC-EMC-DEC mixed solvent that is injected dibenzoyl peroxide and the 90wt% of the TEG dimethylacrylate that contains 9 wt%, 1wt% on the housing with respect to pole piece by the position of adhesive plaster parcel; Wherein, the weight ratio of EC:EMC:DEC is 4:3:3; 75 ℃ are heated 60min down, and heating causes second polymerisation in solution and forms gel, obtains lithium ion battery A3.
Embodiment 4
With barrier film and positive and negative electrode material (for example: LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; With the pole piece bottom, the coiling end sticks transparent rubberized fabric, and after the first liquid injection port territory was reserved at the top of pole piece, all the other positions stuck on a piece of adhesive tape; Contain LiPF from the injection of first liquid injection port
6-LiBF
4First solution of/EC-EMC-DEC-VC wherein, mixes lithium salts LiPF
6-LiBF
4Concentration be 1mol/L, the weight ratio of EC:EMC:DEC:VC is 4:3:2.5:0.5, after the ageing, battery is carried out precharge; Then from second liquid injection port; Be to be contained the polyethylene glycol dimethacrylate of 5 wt%, azobisisobutyronitrile and the DEC of 94wt% and second solution of TBP mixed solvent of 1wt% with respect to pole piece by the position injection of adhesive plaster parcel on the housing; Wherein, the weight ratio of DEC:TMP is 3:1; 80 ℃ are heated 45min down, and heating causes second polymerisation in solution and forms gel, obtains lithium ion battery A4.
Embodiment 5
With barrier film and positive and negative electrode material (for example: LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; With the bottom of pole piece, the coiling end sticks transparent rubberized fabric, and after first liquid injection port was reserved at the top of pole piece, transparent rubberized fabric was sticked in all the other positions; From second liquid injection port; Be to be contained the polyethylene glycol dimethacrylate of 5 wt%, azobisisobutyronitrile and the DEC of 94wt% and second solution of TMP mixed solvent of 2wt% with respect to pole piece by the position injection of adhesive plaster parcel on the housing, wherein the weight ratio of DEC:TMP is 1:1; 85 ℃ are heated 30min down, and heating causes second polymerisation in solution and forms gel; Inject from first liquid injection port then and contain LiPF
6With first solution of EC-EMC-DEC-VC-FEC organic solvent, wherein, LiPF
6Concentration is 1mol/L, and the weight ratio of EC:EMC:DEC:VC:FEC is 4:2:2.5:0.5:1, after the ageing, battery is carried out precharge, accomplishes formation process, promptly obtains lithium ion battery A5.
Embodiment 6
With barrier film and positive and negative electrode material (LiCoO
2Positive pole/barrier film/graphite cathode), be wound into Battery Pole Core; With the bottom of pole piece, the coiling end sticks transparent rubberized fabric, and after first liquid injection port was reserved at the top of pole piece, transparent rubberized fabric was sticked in all the other positions; From second liquid injection port; Be to be contained the glycol dimethylacrylate of 8wt%, azobisisobutyronitrile and the DEC of 90wt% and second solution of TBP mixed solvent of 2wt% with respect to pole piece by the position injection of adhesive plaster parcel on the housing, wherein the weight ratio of DEC:TBP is 2:3; Heat 20min down at 90 ℃, heating causes second polymerisation in solution and forms gel; Inject from first liquid injection port then and contain LiPF
6First solution of-LiBOB and EC-EMC-DEC-VC-FEC wherein, mixes lithium salts LiPF
6-LiBF
4Concentration be 1.5mol/L, the weight ratio of EC:EMC:DEC:VC:FEC is 3:2:3.5:0.5:1, after the ageing, behind battery pre-charging, accomplishes formation process, promptly obtains lithium ion battery A5.
Performance test
Loop test: adopt prepared lithium ion battery, carry out the test of normal temperature 1C electric current charge-discharge performance.Write down the surplus ratio of battery capacity after 400 times.The discharge capacity of battery before capability retention=(discharge capacity of battery before the discharge capacity-circulation of the battery after 400 times of circulating)/circulation wherein, test result is seen table 1.
Table 1
| Sample number into spectrum | A1 | A2 | A3 | A4 | | A6 | B | 1 | B2 |
| Battery capacity surplus ratio (%) after 400 times circulates | 83% | 85% | 84% | 87% | 87% | 90% | 27% | 71.6% |
From table 1, can see; The lithium ion battery that the preparation method of employing embodiment of the invention 1-6 makes is compared to the lithium ion battery of Comparative Examples 1-2 preparation; Have better cycle performance, and, because the housing and the gel between the pole piece of the lithium ion battery that the preparation method of embodiment 1-6 makes can absorb the liquid electrolyte that spills; Thereby, have good safety performance simultaneously.
Those skilled in the art know easily; The above is merely preferred embodiment of the present invention; Not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. lithium ion battery; Comprise: housing, be contained in the pole piece in the housing; Said pole piece comprises positive pole, negative pole, between positive and negative electrode barrier film, it is characterized in that: contain liquid electrolyte in the said pole piece, be filled with gel between said pole piece and the housing.
2. lithium ion battery according to claim 1; It is characterized in that: said pole piece by positive pole, negative pole, membrane coil between positive and negative electrode around forming; Be coated with adhesive plaster on the pole piece behind the coiling and make and be formed for accommodating the seal cavity of liquid electrolyte in the pole piece, and on pole piece, leave first liquid injection port that is used to inject liquid electrolyte.
3. lithium ion battery according to claim 2 is characterized in that: said first liquid injection port is located at the top of pole piece, and first liquid injection port passes adhesive plaster; Said adhesive plaster is coated on the coiling end of the pole piece behind the coiling, the bottom of pole piece and the zone of top except that first liquid injection port of pole piece.
4. according to claim 2 or 3 described lithium ion batteries, it is characterized in that: said housing is provided with second liquid injection port that is used to inject second solution that forms gel, and said second liquid injection port is away from said first liquid injection port.
5. lithium ion battery according to claim 1 is characterized in that: said gel is the polymer of the acrylic ester monomer polymerization formation of one or more unsaturated double-bonds.
6. the preparation method of a lithium ion battery, it is characterized in that: said preparation method comprises the steps:
Step 1, on pole piece, coat adhesive plaster, make and form seal cavity in the pole piece;
Step 2, earlier liquid electrolyte is injected the seal cavity of pole piece, carry out precharge and change into, then second solution is injected between housing and the pole piece, the heating initiated polymerization forms gel between pole piece and housing; Perhaps earlier second solution is injected between housing and the pole piece, the heating initiated polymerization forms gel between pole piece and housing, then liquid electrolyte is injected the seal cavity of pole piece, carries out precharge and changes into.
7. the preparation method of lithium ion battery according to claim 6, it is characterized in that: the temperature of said heating initiated polymerization is 60-100 ℃, the time is 10-120min.
8. the preparation method of lithium ion battery according to claim 6; It is characterized in that: said liquid electrolyte contains the lithium salts and first solvent; The concentration of lithium salts is 0.5-1.5mol/L; Wherein, said lithium salts is selected from a kind of or two or more in lithium hexafluoro phosphate, lithium perchlorate, LiBF4, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfoamido lithium, the biethyl diacid lithium borate; The carbonates solvent that said first solvent is straight chain or ring-type.
9. the preparation method of lithium ion battery according to claim 6; It is characterized in that: said second solution comprises unsaturated monomer, initator and second solvent; Said unsaturated monomer is the acrylic ester monomer that contains one or more unsaturated double-bonds; Said thermal initiator is selected from a kind of or two or more in dibenzoyl peroxide, azobisisobutyronitrile, the accelerine, and the said second solvent package carbonate-containing kind solvent is or/and halo carbonates solvent; Total weight with second solution is a benchmark, and the content of said unsaturated monomer is 3wt-30wt%, and the content of said initator is 0.5wt-3wt%, and the content of second solvent is 67wt-96.5wt%.
10. the preparation method of lithium ion battery according to claim 9; It is characterized in that: said second solvent also comprises organic phosphorus compound; Said organic phosphorus compound are selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributyl phosphate, tricresyl phosphate (2-chloroethyl) ester, methyl-phosphoric acid dimethyl ester, vinyl ethyl phosphonic acid ester, a kind of or two or more in the hexamethyl phosphoramide.
11. the preparation method of lithium ion battery according to claim 6; It is characterized in that: with positive pole, negative pole, membrane coil between positive and negative electrode around forming pole piece; Coating adhesive plaster on the pole piece behind coiling makes and forms seal cavity in the pole piece; And on pole piece, be reserved with first liquid injection port that is used to inject liquid electrolyte, in pole piece, inject liquid electrolyte through said first liquid injection port.
12. the preparation method of lithium ion battery according to claim 11 is characterized in that: second liquid injection port is set on housing, and said second liquid injection port is injected second solution away from said first liquid injection port through said second liquid injection port in housing.
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