The utility model content
In view of this, the purpose of this utility model is to provide a kind of high security lithium ion secondary battery, it is stable and reliable for performance, can solve electrode diaphragm and melt the battery short circuit problem that causes, avoid the generation of security incident, can have good security performance, guarantee long-time normal use of lithium ion battery, extend the useful life of lithium rechargeable battery, thereby have market application foreground widely, be of great practical significance.
For this reason, the utility model provides a kind of high security lithium ion secondary battery, includes seal casinghousing, includes anode, negative electrode and electrolyte in described seal casinghousing;
The surface of described anode and/or negative electrode has the single or multiple lift insulator film, and described insulator film possesses loose structure.
Wherein, the material of described negative electrode comprises at least a in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, lithium cobalt nickel manganese oxide and lithium iron phosphate;
The material of described anode comprises at least a in graphite, hard carbon, soft carbon, silica-base material and tin-based material.
Wherein, described insulator film is the insulator film that includes ceramic insulating layer and adhesive layer and possess loose structure.
Wherein, the material of described ceramic insulating layer is oxide ceramic material or insulative nitride material;
Described oxide ceramic material comprises at least a in aluminium oxide, titanium oxide and silica, and described insulative nitride material is silicon nitride.
Wherein, the oxide ceramic material that comprises in described ceramic insulating layer or the particle size range of insulative nitride material are 1 ~ 15 μ m.
Wherein, described lithium ion secondary electricity is laminated battery plate.
Wherein, described anode and negative electrode are undertaken stacked together by cross layered mode.
The technical scheme that is provided by above the utility model as seen, compared with prior art, the utility model provides a kind of high security lithium ion secondary battery, it is stable and reliable for performance, can solve electrode diaphragm and melt the battery short circuit problem that causes, avoid the generation of security incident, can have good security performance, guarantee long-time normal use of lithium ion battery, extend the useful life of lithium rechargeable battery, thereby have market application foreground widely, be of great practical significance.
Embodiment
In order to make those skilled in the art person understand better the utility model scheme, the utility model is described in further detail below in conjunction with drawings and embodiments.
The utility model provides a kind of high security lithium ion secondary battery, includes seal casinghousing, includes anode, negative electrode and electrolyte in described seal casinghousing.
In the utility model, described seal casinghousing can be the housing that adopts aluminium, steel or plastic cement material to make, and perhaps described seal casinghousing can be the plastic film shell.
In the utility model, described electrolyte can include polyesters solvent and lithium salts solute, perhaps can be other nonaqueous electrolytic solutions.For example, described polyesters solvent can be methyl ethyl carbonate (EMC), and described lithium salts solute can be lithium hexafluoro phosphate (LiPF
6).
In the utility model, described anode and negative electrode have all possessed two kinds of functions, namely as the insulator between stored energy body and reflexive electrode (opposing electrode).
Need to prove, for the utility model, described seal casinghousing is used for guaranteeing that the inside battery structure is hedged off from the outer world; Described used for electrolyte is in the transmitting medium that ion is provided; Described anode and negative electrode not only all as the stored energy body, also possess electronic isolation each other simultaneously;
In the utility model, for lithium rechargeable battery of the present utility model, in order to allow anode and negative electrode can be used as the energy storage body, the material of described negative electrode can be the transition metal oxidate for lithium, specifically can comprise at least a in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, lithium cobalt nickel manganese oxide and lithium iron phosphate; The material of described anode can comprise that at least a in graphite, hard carbon, soft carbon, silica-base material and tin-based material, these materials are the material that possesses storage lithium ability.
In the utility model, in order to allow described anode and negative electrode can be used as insulator between the reflexive electrode, be electronic isolation mutually between the electrode of opposed polarity, on specific implementation, the surface of described anode and/or negative electrode (being at least one in anode and negative electrode) has the single or multiple lift insulator film.
In the utility model, described insulator film can be the porous composite construction of ceramic insulating layer and adhesive layer, and being described insulator film is the insulator film that includes ceramic insulating layer and adhesive layer and possess loose structure (namely having a plurality of holes).
On specific implementation, the material of described ceramic insulating layer can be oxide ceramic material or insulative nitride material, described oxide ceramic material specifically can comprise at least a in aluminium oxide, titanium oxide and silica, and described insulative nitride material can be silicon nitride.
Need to prove, for the utility model, the particle size range of the ceramic particle that comprises in described ceramic insulating layer (as oxide ceramic material or insulative nitride material) is 1 ~ 15 μ m, can not use the ceramic particle material lower than 500nm, when guaranteeing that described insulator film forms, possess enough spaces between adjacent ceramic particle and stay hole, by these holes, can fill the electrolyte of using for conducting ion.Therefore, the lithium rechargeable battery that provides for the utility model, the anode that it comprises and negative electrode, on the one hand can intercept each other electrical conductivity by insulator film, avoid occurring the short circuit problem between opposing electrode, hold electrolyte because insulator film has possessed enough holes on the other hand, thereby can carry out ionic conduction by the electrolyte in the insulator film hole, and then improve the necessary ionic conductance of lithium rechargeable battery work.
Also need to prove for the utility model, if the hole that forms between two adjacent ceramic particles is too little, enough ionic conductivities will do not possessed.Therefore, on specific implementation, the particle size range of described ceramic particle (as oxide ceramic material or insulative nitride material) is preferably 3 ~ 5 μ m, to guarantee having enough holes and better processing characteristics between the adjacent ceramic particle.
In the utility model, what described adhesive layer adopted selects and the opposite polarity classification of electrode (male or female) of being fixed with glue is general, thereby prevents in preparation process, to electrode, ceramic insulating film surface corroding.
In the utility model, on specific implementation, in order to allow described insulator film fix on the surface of anode and/or cathode electrode, the mode that can adopt roller coating, spraying and heat seal to shift makes insulator film fix at anode and/or cathode electrode surface moulding.
In the utility model, on specific implementation, in order to form hole on described insulator film, can adopt the mode of solvent flashing, in the film formed process of insulator, by drying volatile solvent, make it to box out.
In the utility model, the preparation process of loose structure on described insulator film (namely forming a plurality of holes) can for:
The first step: will comprise the colloidal sol roller coating of ceramic insulating layer material particle and easy volatile solvent on a kind of base material;
Second step: then baking makes the easy volatile solvent in colloidal sol be evaporated, thereby forms a plurality of holes (namely forming loose structure) in the upper preparation of formed insulator film (being ceramic insulating layer material film).
In the utility model, on specific implementation, the thickness range of described insulator film is preferably 15 ~ 60 μ m, if thickness is less than 15 μ m, described insulator film can not possess enough electronic isolations, if thickness is greater than 60 μ m, described insulator film can not possess enough ionic conductivities, thereby can't provide lithium rechargeable battery necessary ionic conduction.For the utility model, the insulation property of described insulator film will reach the Mohm(megohm) rank, guarantee electronic isolation performance like this.
In the utility model, on specific implementation, the integrated structure of these two kinds of electrodes of the anode of described lithium rechargeable battery and negative electrode, can select stacked and winding-structure, that is to say, described lithium rechargeable battery can be laminated battery plate and coiled battery, specifically is preferably laminated battery plate, purpose is to reduce the destruction to insulator film, guarantees that the combination between the electrodes such as the anode of battery and negative electrode is tight.
In the utility model, on specific implementation, can combine by the hot pressing mode of HTHP between described anode and negative electrode, form positive electrode, insulator film and negative electrode composite construction.The temperature that described hot pressing is adopted is preferably 80 ℃, the pressure that described hot pressing is adopted is preferably 0.2MPa, the time range that described hot pressing continues can be 1 ~ 10min, like this, the utility model both can guarantee the heat bonding effect between described anode and negative electrode, improve again production efficiency, and then reduced the production cost of battery.
Need to prove, for the lithium rechargeable battery that the utility model provides, it can guarantee that battery at the short circuit problem that does not occur under high temperature more than 160 ℃ between reflexive electrode (opposing electrode), has improved battery security.Simultaneously, the manufacturing process that provides based on above-mentioned the utility model, can guarantee that the insulator film in the lithium rechargeable battery has possessed enough holes and held electrolyte, and then provide the lithium rechargeable battery normal operation necessary ionic conductance by the electrolyte in hole.
In addition, described anode and negative electrode combine by hot pressing mode, can so that the electrode structure of lithium ion battery is more stable, guarantee that battery has excellent cycle performance.
The concrete preparation process of a kind of high security lithium ion secondary battery that the utility model provides is described below by a specific embodiment.
1, selection material step.Select the solid oxide aluminium Al of α shape
2O
3Material as ceramic insulating layer in insulator film (need to prove described solid oxide aluminium Al
2O
3Can be the Al of α type
2O
3Al with the γ type
2O
3In at least a), described solid oxide aluminium Al
2O
3The average grain diameter of particle (being D50) scope is preferably 2 μ m ~ 10 μ m; Simultaneously, described aluminium oxide Al
2O
3The adhesive layer of particle can be solid-state polyacrylic acid glue (need to prove, both can be polypropylene type glue, can also be solid-state Kynoar class glue, for example solid-state Kynoar PVDF) with glue.At this moment, for the utility model, described aluminium oxide Al
2O
3Mass ratio between particle and polyacrylic acid glue can be 95:5, wherein, also comprises containing the pore-creating thing: liquid silane coupler, described silane coupler and described aluminium oxide Al
2O
3Mass ratio between particle is 1:100;
At this moment, the material of negative electrode is chosen as oxide material of lithium, cobalt, nickel and manganese, and bonds with Kynoar PVDF.The material of anode is chosen as the Delanium material, and use base styrene butadiene rubber sbr bonding.
2, preparation battery step.The utility model comprises the following steps in order to form insulator film on the surface of anode:
At first, make colloidal sol with Kynoar PVDF and 1-METHYLPYRROLIDONE (NMP), the solid content that requires described colloidal sol is 3%, is used for as standby colloidal sol;
Then, aluminium oxide Al
2O
3This three's solute of particle, polyacrylic acid glue and silane coupler is with solvent NMP(N-methyl pyrrolidone) to dissolve, it is 40% aluminium oxide Al that configuration forms solid content
2O
3Colloidal sol;
Then, aluminium oxide Al
2O
3The colloidal sol roller coating is to PET base material (being polyethylene terephthalate PET polyester film), and the thickness that requires the insulator film of roller coating is 35 μ m, then with the temperature baking of 120 ℃, makes aluminium oxide Al
2O
3Colloidal sol becomes gel, and allows liquid NMP volatilization, finally forms hole on formed pellumina, and as shown in Figure 1, described pellumina 2 is formed on described PET base material 1 surface, has a plurality of holes 3 on described pellumina 2;
then, as shown in Figure 2, after rolling with anode unreeling shaft 5 antianode pole pieces, the pellumina of above-mentioned formation is placed into the surface of anode, simultaneously in put procedure, with base material unreeling shaft 6 and base material Scroll 7, PET base material 1 is peeled away from pellumina, and with the standby colloidal sol of lance ejection between the surface of pellumina 2 and anode 10, form the standby glue layer 4 of one deck, thereby formation anode material, " composite construction " of standby sol layer and pellumina, then toast with the temperature of 120 ℃, make liquid NMP volatilization, form equally hole 3 on standby glue layer 4,
Then, the anode 10 that will have pellumina is undertaken stacked with negative electrode 20 by cross layered mode, reach the needed number of plies of manufacturer of laminated battery plate, as shown in Figure 3, then adopt hot pressing mode that the anode 10 that the surface has pellumina 2 is combined with negative electrode 20, the pressure that adopts during hot pressing is 0.2MPa, and the temperature of hot pressing is 80 ℃, hot pressing time is 1 minute, thereby allows the surface have between the anode 10 of pellumina 2 and negative electrode 20 heat bonding firmly;
At last, then put in seal casinghousing (as the aluminum plastic film housing), and injection electrolyte, allow negative electrode and anode and insulator film Electolyte-absorptive, the final lithium rechargeable battery that forms a kind of high security, not only can intercept electrical conductivity by insulator film between the anode that it has and negative electrode, can also carry out ionic conduction by the electrolyte in the insulator film hole simultaneously, guarantee the serviceability of lithium ion battery.
Therefore, the technical scheme that provides based on above-mentioned the utility model and embodiment are as can be known, the utility model provides a kind of high security lithium ion secondary battery, this lithium rechargeable battery comprises seal, electrolyte, opposite polarity electrode (negative electrode, anode), by cross layered or reel and to combine, be filled with electrolyte between anode and negative electrode between anode and negative electrode, then by seal integral sealing, draw negative electrode and anode water conservancy diversion terminal, and then form a cell body.For the utility model, owing to not only can intercepting electrical conductivity by insulator film between anode and these two reversed polarity electrodes of negative electrode, can also carry out ionic conduction by the electrolyte in the insulator film hole, in described anode and negative electrode, the surface of at least one has the single or multiple lift insulator film simultaneously, described insulator film can be combined closely with electrode, thereby guaranteed that battery of the present utility model in making and use procedure, possesses enough structural stabilities.
For the lithium rechargeable battery that the utility model provides, the insulating bodies film that has on its anode and/or cathode surface will possess enough porositys, is used for filling the electrolyte that ionic conduction is used.Battery manufacturing process of the present utility model comprises the techniques such as insulator film preparation, insulator film pore-creating and battery electrode heat bonding.Therefore, battery for the utility model preparation, it can remove traditional plastics (polyolefin) barrier film, adopt resistant to elevated temperatures insulator film, can improving at high temperature, plastic diaphragms melts the cell safety that causes, simultaneously, owing to firmly anode and these two electrodes of negative electrode being fixed, the useful life that therefore can improve lithium rechargeable battery.
In sum, compared with prior art, the utility model provides a kind of high security lithium ion secondary battery, and it is stable and reliable for performance, can solve electrode diaphragm and melt the battery short circuit problem that causes, avoid the generation of security incident, can have good security performance, guarantee long-time normal use of lithium ion battery, extend the useful life of lithium rechargeable battery, thereby have market application foreground widely, be of great practical significance.
The above is only preferred implementation of the present utility model; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the utility model principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection range of the present utility model.