Embodiment
According to lithium ion battery provided by the invention, the thickness of described ceramic diaphragm is the 5-60 micron, is preferably the 15-40 micron.
The porosity of described ceramic diaphragm refers to the area that the lip-deep hole of ceramic diaphragm is shared and the ratio of film total surface area, for gas permeability and the assurance electrolyte that guarantees described ceramic diaphragm can fully permeate the electrode material that is coated on the positive and negative electrode pole piece of barrier film both sides with wetting, the porosity of described ceramic diaphragm is 20-90%, is preferably 40-80%; The aperture of described ceramic diaphragm is meant the diameter of circular hole or class circular hole, and under the preferable case, the aperture of described ceramic diaphragm is the 20-200 micron, more preferably the 50-150 micron.
Described ceramic diaphragm can be the ceramic diaphragm that has above-mentioned thickness, porosity and aperture arbitrarily.Under the preferable case, described ceramic diaphragm is to be the 20-200 micron by diameter, and the tow braiding that is preferably the 50-120 micron forms, and described tow comprises the 5-50 root, and being preferably 10-30 root diameter is the 1-15 micron, is preferably the microfilament bar of 5-10 micron; Described microfilament bar comprises the 100-500 root, and being preferably 200-300 root diameter is the 0.01-0.10 micron, is preferably the ceramic hollow microfilament of 0.02-0.04 micron.Such ceramic diaphragm has better pliability, is beneficial to coiling.Described ceramic diaphragm can be commercially available, and also can make the microfilament bar with ceramic hollow microfilament, forms tow by the microfilament bar again, obtains described barrier film by the tow braiding at last.
The material of forming described ceramic diaphragm can be various existing materials, under the preferable case, described ceramic diaphragm contains zirconia and yittrium oxide, is benchmark with the total weight of this ceramic diaphragm, described zirconic content is 80-95 weight %, and the content of yittrium oxide is 5-20 weight %.
Because described ceramic diaphragm has higher melt temperature, especially with the zirconia ceramic diaphragm of main component, because zirconic fusing point is 2715 ℃, because its fusing point height, chemical property are stablized, fusion and decomposition can not take place in the ceramic diaphragm that therefore with the zirconia is main component under the high temperature of inside battery, and can well play the effect of isolating anodal and negative pole, positive active material and negative electrode active material are come in contact, thereby guaranteed the good high-temperature stability of lithium ion battery.
Described ceramic diaphragm is arranged between positive plate and the negative plate positive plate and negative plate is separated, and has electrical insulation capability and liquid retainability energy.
The preparation method of kalium ion battery provided by the invention comprises positive pole and the negative pole for preparing battery, and positive pole, negative pole and barrier film are prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, and wherein, described barrier film is a ceramic diaphragm provided by the invention.
Described electrode group is by membrane layer the described positive pole for preparing and negative pole to be twined to separate to obtain, stacked, the method for winding of the membrane layer between positive pole and negative pole are conventionally known to one of skill in the art, for example, barrier film provided by the invention and electrode slice are formed takeup type electrode group through the back of reeling again according to the stacked electrode group of the stacked formation of the order of barrier film, negative plate or positive plate, barrier film, positive plate or negative plate or with aforementioned stacked electrode group, in electrolyte is sealed in battery container.
Described battery container can be the various housings that are applicable to each sharp size battery, and as package compound film shell, metal square shell or round metal cylindricality shell, those skilled in the art can be easy to select as required suitable battery container.
The barrier film that the present invention only relates to battery improves, and the The Nomenclature Composition and Structure of Complexes of battery other parts is not particularly limited.
Consisting of of described positive pole is conventionally known to one of skill in the art.In general, positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body that described positive electrode comprises positive active material, conductive agent and anodal adhesive.
Described positive active material is not particularly limited, and can be the positive active material of the embedded removal lithium embedded of this area routine, a profit or its mixture: the Li in the preferred following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).
Described anodal conductive agent is not particularly limited, and can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Weight with positive active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The kind of described anodal adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), polyvinyl alcohol, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, the hydroxyethylcellulose.In general, according to the difference of used anodal adhesive kind, be benchmark with the weight of positive active material, the content of anodal adhesive is 0.5-8 weight %, is preferably 1-5 weight %.
Positive electrode collector can be positive electrode collector conventional in the lithium ion battery, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.
The preparation method of described positive pole can adopt conventional preparation method.For example, with described positive active material, conductive agent and adhesive and solvent, apply and/or be filled on the described collector body, drying is rolled or is not rolled, and can obtain described positive pole.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector body to get final product.In general the weight with positive active material is benchmark, and the content 30-80 weight % of described solvent is preferably 35-60 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Consisting of of described negative pole is conventionally known to one of skill in the art.In general, negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base that described negative material comprises negative electrode active material and negative pole adhesive.
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, material with carbon element for example, described material with carbon element be selected from non-graphitized charcoal, graphite or the charcoal that obtains by high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon in one or more.Described organic polymer sinter can be by with products therefrom after sintering such as phenolic resins, epoxy resin and the charing.
The kind of described negative pole adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, the polyvinyl alcohol; In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of negative pole adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Described negative material can also comprise that conductive agent to increase the conductivity of electrode, reduces the internal resistance of cell.Described conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as in carbon black, nickel powder, the copper powder one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0-12 weight %, is preferably 2-10 weight %.
The negative pole conducting base can be for negative pole conducting base conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as the negative pole conducting base in specific embodiments of the present invention.
The preparation method of described negative pole can adopt conventional preparation method.For example, with negative material and solvent, apply and/or be filled on the described conducting base, drying is rolled or is not rolled, and can obtain described negative pole.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general, be benchmark with the weight of negative electrode active material, the content of described solvent is 100-150 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.For example, the temperature of described drying is generally 100-150 ℃.
Described electrolyte can be non-water liquid electrolyte or gel state electrolyte.
Described gel state electrolyte is not particularly limited, and can use the gel state electrolyte of this area routine, such as the basic gel state electrolyte of PVdF (poly-difluoroethylene) etc.
Nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, potassium tetrafluoroborate, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour, the concentration of electrolyte be generally 0.1-2.0 rub/liter.
According to the preparation method of lithium ion battery provided by the invention, except barrier film adopted ceramic diaphragm provided by the invention, other step was conventionally known to one of skill in the art.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This embodiment illustrates the preparation of kalium ion battery provided by the invention.
(1) Zheng Ji preparation
With the anodal active component LiCoO of 100 weight portions
2, 5 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 60 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, roll-in is cut on cutting machine and obtain being of a size of 52 millimeters * 32 millimeters * 130 microns positive pole afterwards, wherein contains the anodal material of 0.65 gram.
(2) preparation of negative pole
The big right graphite of 100 weight portion negative electrode active materials, 5 weight portion adhesive polytetrafluoroethylene (PTFE)s are joined in the 100 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on the thick 12 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 53 millimeters * 32 millimeters * 140 microns negative pole, wherein contain 0.3 gram negative pole material.
(3) preparation of electrode group
With thickness is 20 microns, voidage is 40%, average pore size be 100 microns (pore diameter range is the 80-120 micron) ceramic diaphragm (the zirconia ceramics barrier film that Guangzhou Xinlaifu Magnetoelectric Co. Ltd. produces, the zirconia content of described ceramic diaphragm is 92 weight %, yittrium oxide content is 8 weight %.Described ceramic diaphragm is that diameter that 0.02 micron ceramic hollow microfilament is formed is 5 microns a microfilament bar by 250 diameters, and then to form diameter by 15 such microfilament bars be that 75 microns tow braiding obtains), cut into 55 * 33 millimeters diaphragm.The above-mentioned diaphragm that obtains, positive plate and negative plate is stacked successively according to the order of barrier film/positive plate/barrier film/negative plate, make the electrode group that is of a size of 3.2 * 33 * 55 millimeters.
(4) assembling of battery
LiPF6 and ethylene carbonate (EC), diethyl carbonate (DEC) and DMC (dimethyl carbonate) are configured to the solution that LiPF6 concentration is 1.0 mol (wherein, the volume ratio of EC, DEC and DMC is 1: 1: 1), obtain nonaqueous electrolytic solution.The package compound film with PET polyester/NY nylon/AL aluminium foil/CPP hydrostomia polypropylene multi-layer structure that is made of macromolecule membrane and metal forming that the electrode group that (3) are obtained is put into an end opening strikes out the battery case of the groove that has 3.5 * 33 * 55 millimeters, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, the capacity of making after the sealing is 800mAh, and outside dimension is 3.8 * 35 * 62 millimeters laminated structure flexible packing lithium ion secondary battery A1.
Embodiment 2
This embodiment illustrates the preparation of kalium ion battery provided by the invention.
(1) Zheng Ji preparation
With the anodal active component LiCoO of 100 weight portions
2, 5 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 60 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, roll-in is cut on cutting machine and obtain being of a size of 52 millimeters * 360 millimeters * 130 microns positive pole afterwards, wherein contains the anodal material of 6.5 grams.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 5 weight portion adhesive polytetrafluoroethylene (PTFE)s are joined in the 100 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on the thick 12 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 53 millimeters * 325 millimeters * 140 microns negative pole, wherein contain 3.0 gram negative pole material.
(3) preparation of electrode group
With thickness is 20 microns, voidage is 60%, average pore size be 100 microns (pore diameter range is the 80-120 micron) ceramic diaphragm (the zirconia ceramics barrier film that Guangzhou Xinlaifu Magnetoelectric Co. Ltd. produces, the zirconia content of described ceramic diaphragm is 92 weight %, yittrium oxide content is 8 weight %.Described ceramic diaphragm is that diameter that 0.02 micron ceramic hollow microfilament is formed is 5 microns a microfilament bar by 250 diameters, and then to form diameter by 20 such microfilament bars be that 100 microns tow braiding obtains) cut into 55 * 740 millimeters diaphragm.The above-mentioned diaphragm that obtains, positive plate and negative plate are wound into the electrode group that is of a size of 3.2 * 33 * 55 millimeters according to the order of barrier film/negative plate/barrier film/positive plate after stacked successively.
(4) assembling of battery
LiPF6 and ethylene carbonate (EC), diethyl carbonate (DEC) and DMC (dimethyl carbonate) are configured to the solution that LiPF6 concentration is 1.0 mol (wherein, the volume ratio of EC, DEC and DMC is 1: 1: 1), obtain nonaqueous electrolytic solution.The electrode group that (3) are obtained is put into the aluminum metal battery case of an end opening, and injects above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, and the capacity of making after the sealing is 800mAh, and outside dimension is 3.8 * 35 * 57 millimeters square lithium ion secondary battery A2.
Embodiment 3
This embodiment illustrates the preparation of kalium ion battery provided by the invention.
(1) Zheng Ji preparation
With the anodal active component LiCoO of 100 weight portions
2, 5 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 60 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, roll-in is cut on cutting machine and obtain being of a size of 52 millimeters * 360 millimeters * 125 microns positive pole afterwards, wherein contains the anodal material of 6.1 grams.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 5 weight portion adhesive polytetrafluoroethylene (PTFE)s are joined in the 100 weight portion n-formyl sarcolysine base pyrrolidones (NMP), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on the thick 12 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 53 millimeters * 325 millimeters * 135 microns negative pole, wherein contain 2.8 gram negative pole material.
(3) preparation of electrode group
With thickness is 30 microns, voidage is 80%, average pore size be 100 microns (pore diameter range is the 80-120 micron) ceramic diaphragm (the zirconia ceramics barrier film that Guangzhou Xinlaifu Magnetoelectric Co. Ltd. produces, the zirconia content of described ceramic diaphragm is 92 weight %, yittrium oxide content is 8 weight %.Described ceramic diaphragm is that diameter that 0.04 micron ceramic hollow microfilament is formed is 7 microns a microfilament bar by 200 diameters, and then to form diameter by 20 such microfilament bars be that 120 microns tow braiding obtains) cut into 55 * 740 millimeters diaphragm.The above-mentioned diaphragm that obtains, positive plate and negative plate is stacked successively according to the order of barrier film/negative plate/barrier film/positive plate, make the electrode group that is of a size of 3.2 * 33 * 55 millimeters.
(4) assembling of battery
LiPF6 and ethylene carbonate (EC), diethyl carbonate (DEC) and DMC (dimethyl carbonate) are configured to the solution that LiPF6 concentration is 1.0 mol (wherein, the volume ratio of EC, DEC and DMC is 1: 1: 1), obtain nonaqueous electrolytic solution.The package compound film with PET polyester/NY nylon/AL aluminium foil/CPP hydrostomia polypropylene multi-layer structure that is made of macromolecule membrane and metal forming that the electrode group that (3) are obtained is put into an end opening strikes out the battery case of the groove that has 3.5 * 33 * 55 millimeters, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, the capacity of making after the sealing is 750mAh, and outside dimension is 3.8 * 35 * 62 millimeters laminated structure flexible packing lithium ion secondary battery A3.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference lithium ion battery.
Prepare reference lithium ion battery AC1 according to the method for embodiment 1 and the content of each material, different is, is 20 microns with thickness, and voidage is that 40% PE individual layer microporous barrier replaces the ceramic diaphragm among the embodiment 1.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference lithium ion battery.
Prepare reference lithium ion battery AC2 according to the method for embodiment 2 and the content of each material, different is, is 20 microns with thickness, and voidage is that three layers of microporous barrier of PP/PE/PP of 60% replace the ceramic diaphragm among the embodiment 2.
Comparative Examples 3
The preparation of this Comparative Examples explanation reference lithium ion battery.
Prepare reference lithium ion battery AC3 according to the method for embodiment 3 and the content of each material, different is, is 30 microns with thickness, and voidage is that three layers of microporous barrier of PP/PE/PP of 40% replace the ceramic diaphragm among the embodiment 3.
Performance test
The lithium ion battery AC1-AC3 that lithium ion battery A1-A3 that stove heat testing method below adopting obtains embodiment 1-3 respectively and Comparative Examples 1-3 obtain carries out the test of battery safety.
The test of stove heat:
Adopt lithium ion battery test cabinet above-mentioned kalium ion battery charge (1C constant-current constant-voltage charging, the upper limit of charging 4.2V, cut-off current 20mA).Then battery is put in the high temperature furnace, the speed raising furnace temperature with 5 ℃ of per minute risings is elevated to 150 ℃, 160 ℃ and 170 ℃ up to temperature.Respectively battery was kept 60 minutes phenomenons such as whether the observation battery occurs smoldering, burning, blast down at 150 ℃, 160 ℃ and 170 ℃.The result is as shown in table 1.
Table 1
|
150 ℃ of stove heat test phenomenons |
160 ℃ of stove heat test phenomenons |
170 ℃ of stove heat test phenomenons |
Embodiment 1 |
Do not have smolder, burning, explosion phenomenon |
Do not have smolder, burning, explosion phenomenon |
Do not have smolder, burning, explosion phenomenon |
Embodiment 2 |
Do not have smolder, burning, explosion phenomenon |
Do not have smolder, burning, explosion phenomenon |
Phenomenon appears smoldering |
Embodiment 3 |
Do not have smolder, burning, explosion phenomenon |
Do not have smolder, burning, explosion phenomenon |
Do not have smolder, burning, explosion phenomenon |
Comparative Examples 1 |
Phenomenon appears smoldering |
Appearance is smoldered, combustion phenomena |
Fried phenomenon occurs smoldering, burning |
Comparative Examples 2 |
Occur smoldering, burning, explosion phenomenon |
Occur smoldering, burning, explosion phenomenon |
Occur smoldering, burning, explosion phenomenon |
Comparative Examples 3 |
Do not have smolder, burning, explosion phenomenon |
Appearance is smoldered, combustion phenomena |
Appearance is smoldered, combustion phenomena |
From above-mentioned test result as can be seen, compare with the lithium ion battery of Comparative Examples 1-3 preparation, because what lithium ion battery of the present invention adopted is the excellent ceramic diaphragm of high-temperature stability, thereby the laminated structure flexible packing lithium ion secondary battery of the embodiment of the invention 1, the square potassium ion secondary cell of embodiment 2, the winding flexible packing potassium ion secondary cell of embodiment 3 at high temperature all has excellent high-temperature and pacifies surplus performance, and is better than the lithium ion battery that Comparative Examples 1-3 obtains greatly.