CN1274179A - Button-type secondary lithium ion battery and its manufacture technology - Google Patents
Button-type secondary lithium ion battery and its manufacture technology Download PDFInfo
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Abstract
公开了一种钮扣式锂离子二次电池,它包括含锂化合物正极、石墨负极和隔膜,其中所述含锂化合物正极和石墨负极均是模压成型的。按正极材料的总重量计,所述含锂化合物正极含有80—90重量%含锂化合物,含有5—11重量%导电材料,含有4—10重量%PVDF。按负极材料的总重量计,所述石墨负极含有82—92重量%改性天然石墨,含有4—10重量%导电材料,含有4—8重量%PVDF。还公开了这种电池的制造方法。Disclosed is a button-type lithium ion secondary battery, which comprises a lithium-containing compound positive electrode, a graphite negative electrode and a separator, wherein the lithium-containing compound positive electrode and the graphite negative electrode are all molded. Based on the total weight of the positive electrode material, the lithium-containing compound positive electrode contains 80-90% by weight of lithium-containing compound, 5-11% by weight of conductive material, and 4-10% by weight of PVDF. Based on the total weight of negative electrode materials, the graphite negative electrode contains 82-92% by weight of modified natural graphite, 4-10% by weight of conductive material, and 4-8% by weight of PVDF. A method of manufacturing such a battery is also disclosed.
Description
The present invention relates to button lithium rechargeable battery and preparation method thereof.
Lithium ion battery is another emerging after nickel-cadmium cell and Ni-MH battery small rechargeable heavy-duty battery.This battery had both kept that specific capacity height, the energy density of lithium battery is big, operating voltage is high and advantage such as in light weight, had solved problems such as lithium battery fail safe and cycle life is limited again.
Present many compact electric apparatus (as electronic watch, calculator, camera and video camera etc.) all use button cell.Therefore, industrially many button cells that meet demand have been developed.But, the existing button cell relevant with the lithium metal all be with metal lithium sheet or lithium alloy as the negative active core-shell material of battery because the existence of Li dendrite, for safety, these button cells all are rechargeables not.Promptly discarded after this disposable battery uses up, therefore there are contaminated environment and waste problem of resource, do not meet the trend of environmental protection.
The United States Patent (USP) 549101 of authorizing K.M.Abraham in March, 1996 discloses a kind of laminar battery, and this battery as negative material, is used LiMn with graphite
2O
4As positive electrode, the solid polymer electrolyte that with the acrylonitrile is base is as barrier film, and with the method for laminating positive and negative pole material and membrane layer being forced together is assembled into laminar battery.But the charge/discharge capacity of this battery only is 10mAh.
China Wuhan power emerging power technology company discloses a kind of usefulness and be coated with the button cell that the band method is assembled in October, 1997 in " the 9th national electrochemistry meeting ", its maximum nominal capacity is 25mAh under 1mA constant current charge-discharge condition.But the space availability ratio in the complex forming technology of this battery and the battery case is also low, thereby makes production cost of cells higher, owing to there is electrode holder, makes the capacitance of unit volume descend.
The positive electrode die pressing moulding that present business-like button lithium battery is used, negative material are then directly dashed from the lithium metal sheet material and are shut out.Because the safety problem that Li dendrite brings though the capacity of this battery is high, but is non-rechargeabel.
Therefore the button lithium rechargeable battery that needs a kind of low-cost high power capacity of exploitation, and the manufacture method of this battery.
The purpose of this invention is to provide a kind of button lithium rechargeable battery.It has specific capacity height, advantages such as low cost of manufacture;
It is the manufacture method of the button lithium rechargeable battery of negative material with graphite that another object of the present invention provides a kind of.
The invention provides a kind of button lithium rechargeable battery, it comprises lithium-containing compound positive pole, graphite cathode and barrier film, it is characterized in that described lithium-containing compound positive pole and graphite cathode all are compression moldings.
The present invention also provides a kind of preparation method of button lithium rechargeable battery, and it comprises:
1) forms the lithium-containing compound positive pole;
2) form graphite cathode;
3) described positive pole, negative pole are formed the button lithium rechargeable battery with barrier film;
It is characterized in that described lithium-containing compound positive pole and graphite cathode all are compression moldings.
Illustrate in greater detail the present invention below in conjunction with accompanying drawing.In the accompanying drawing,
Fig. 1 is the profile of the button lithium ion battery of example of the present invention;
Fig. 2 is the charging and discharging curve of the embodiment of the invention 1 button lithium ion battery;
Fig. 3 is the charging and discharging curve of the embodiment of the invention 2 button lithium ion batteries;
Fig. 4 is the charging and discharging curve of the embodiment of the invention 3 button lithium ion batteries;
Fig. 5 show the embodiment of the invention 4 button lithium ion batteries the 5th circulation time capacity with electric current variation;
Fig. 6 is the amount of capacity of the embodiment of the invention 4 button lithium ion batteries after more than 40 circulations under the big current condition.
The invention provides a kind of button lithium rechargeable battery, it comprises lithium-containing compound positive pole, graphite cathode and barrier film, and wherein said lithium-containing compound positive pole and graphite cathode all are compression moldings.
In the present invention, term " button cell " is well-known in the art, can be to be usually used in the battery that electronic watch, calculator etc. have disk or button shape such as it.
Lithium-containing compound of the present invention is anodal without now special, and it can be the positive pole of lithium rechargeable battery as known in the art. For example, can use LiCoO2、LiNi
1-xCo
xO
2(0.2≤x≤1)、LiMn
2O
4、
Li
xV
2O
5、Li
xV
6O
3、Li
xVS
2、Li
xCV
0.5S
2And LixTiS
2Deng, better use the LiMn of spinel structure2O
4, accurate two-dimentional type layer structure LiCoO2Or LiNi0.5Co
0.5O
2As positive electrode active materials. This positive electrode active materials is commercially available. For example, can be with the LiCoO available from German Merck company2, will be available from the LiNi of Jingle Power Source Tech. Co., Ltd., Shanghai0.5Co
0.5O
2And LiCoO2, and available from the LiMn of German Merck company2O
4As positive electrode active materials of the present invention. Those of ordinary skill in the art also can easily synthesize these materials according to methods known in the art.
Above-mentioned lithium-containing compound can be molded into required shape with conductive material and polyvinylidene fluoride (PVDF) powder. The used conductive material of the present invention is known in the art, and its example comprises that for example available from acetylene black and the conventional graphite powder of Shanghai multiple elements chemical power supply factory, wherein the most frequently used is acetylene black; Be used for PVDF of the present invention and be commercially available, for example, available from the PVDF of Shanghai Organic fluoride research institute.
The particle diameter of lithium-containing compound active material of the present invention and conductive material and PVDF powder is without particular limitation, as long as the particle diameter that adopts can reach the object of the invention. The preferably particle diameter of lithium-containing compound active material is the 5-15 micron, and conductive material preferably particle diameter is the 0.1-1 micron, and the preferably particle diameter of PVDF powder is 10 microns.
In positive pole of the present invention, by the gross weight of positive electrode, the content of lithium-containing compound is about the 80-90 % by weight, better is about 85 % by weight; The content of conductive material is about the 5-11 % by weight, better is about 10 % by weight; The content of PVDF is about the 4-10 % by weight, better about 5 % by weight.
The key component of graphite cathode of the present invention is the native graphite of modification. Native graphite is cheap and have extraordinary layer structure, can be inserted by lithium ion well, forms LixC
6Compound. Along with the increase of lithium ion insertion amount, the X value increases to 1 by 0 gradually, and maximum is 1. Can form during insertion different step (stage) layer. The different intercalation platforms that this point can occur from the half-cell charging and discharging curve of routine clearly illustrate out.
But the charging and discharging curve first time of native graphite voltage platform can occur near 0.8V, causes to discharge and recharge rear capacitance loss for the first time. It is generally acknowledged that this is lithium ion when inserting graphite linings for the first time, form passivating film at graphite surface, or solvent inserts etc. altogether, and irreversible procedure causes. The generation of these processes and graphite surface existence-OH ,-the COOH group is relevant, so need to adopt different atmosphere carry out physics or chemical method modification to native graphite, eliminating these groups, thereby suppresses the generation of irreversible procedure.
The method of modifying of native graphite is known in the art. For example, can adopt the methods such as heat treatment under acid, alkali and the various different atmosphere and carbon film parcel, disclose such as Japanese Laid-Open Patent Application 97-326254 and a kind ofly to make RESEARCH OF PYROCARBON or other Compound deposition at graphite surface with vapour deposition process, the reusable heat processing method increases crystallization irregularity degree native graphite is carried out modification.
Native graphite is carried out can improving after the modification pattern on graphite granule surface, remove the impurity in the graphite raw material, the arrangement of adjusting the graphite granule interlayer continues.Graphite can reduce electrolyte to the insertion ability between its carbon-coating after modification is handled, help the embedding of taking off of lithium ion, thereby improves the reversible capacity of material, suppresses non-reversible capacity.
When making negative material of the present invention, the native graphite of modification and electric conducting material and PVDF powder mixing in certain proportion can be put into mould subsequently and is molded into required shape.
In negative material of the present invention, by the total weight of negative material, the content of modified graphite is about 82-92 weight %, is preferably 90 weight %; The content of electric conducting material is about 4-10 weight %, is preferably 5 weight %; The content of PVDF is about 4-8 weight %, is preferably 5 weight %.
The particle diameter of modified graphite of the present invention and electric conducting material and PVDF powder is without particular limitation, as long as the particle diameter that is adopted can reach the object of the invention.Described modified graphite particle diameter preferably is the 1-50 micron, and electric conducting material particle diameter preferably is the 0.1-1 micron, and the particle diameter preferably of PVDF powder is 10 microns.
The raw material of modified graphite of the present invention is commercially available, and for example, the present invention can adopt the native graphite available from Nanshu Graphite Mine, Shandong Prov., uses the described method of Japanese Laid-Open Patent Application 97-326254 that it is carried out the modified graphite that makes after the modification subsequently.
The barrier film of button lithium ion battery of the present invention can be conventional lithium ion battery barrier film, its example comprises, but be not limited to polyethylene film (PE), polypropylene screen (PP), PVDF membrane (PVDF) etc., described barrier film also can be a solid polymer dielectric film, as the graft copolymer (PMMA) of poly-oxireme (PEO), polyacrylonitrile (PAN), PPOX (PPO), polymethacrylic acid etc.
The electrolyte that is used for button lithium rechargeable battery of the present invention can be electrolyte as known in the art, and its example includes, but are not limited to LiPF
6/ EC+DMC, LiPF
6/ EC+DEC and LiAsF
6/ EC+DEC etc., the part by weight of nonaqueous solvents compd E C and DMC or EC and DEC are 1: 1, conducting salt LiPF
6Or LiAsF
6Concentration be to contain 1M in 1 liter of nonaqueous solvents compound.Those of ordinary skill in the art can easily prepare this electrolyte.
The present invention also provides the preparation method of a kind button lithium rechargeable battery, and it comprises
1) forms the lithium-containing compound positive pole;
2) form graphite cathode;
3) anodal and described graphite cathode and barrier film are assembled into the button lithium rechargeable battery with described lithium-containing compound;
It is characterized in that described lithium-containing compound positive pole and graphite cathode all are compression moldings.
At one preferably in the preparation example of the lithium-containing compound positive pole of lithium rechargeable battery of the present invention, with weight ratio 85: 10: 5 LiMn
2O
4, acetylene black and PVDF mix powder sample mix be even, till the PVDF powder that adds pyrrolidones (NMP) subsequently and be stirred in the mixture white disappears, place a period of time make NMP can dissolve the PVDF powder well and with its swelling in the compound of modified graphite and acetylene black powder, then it is molded into required thin cake, puts into the vacuum drying oven oven dry subsequently and get final product.The present invention another preferably in the example, use LiCoO
2Replace LiMn
2O
4Preparation lithium-containing compound positive pole.
The press that is used for mold pressing positive pole of the present invention can be conventional hydraulic press, for example, can use the 769YP-15 type hydraulic press available from device High-tech company of Tianjin section.The pressure that uses during mold pressing is generally 5-25MPa.
When making negative material of the present invention, the native graphite of modification and electric conducting material and PVDF powder mixing in certain proportion can be put into mould subsequently and is molded into required thin cake, the thin cake that will make is again put into vacuum drying oven dries and gets final product.Because native graphite belongs to typical layer structure material, lubrification is fabulous, has pressure graphite to skid off slightly, so the thickness of graphite material is difficult to control.Especially when making button cell,, lossyly slightly will produce bigger thickness error because the consumption of graphite is less.Therefore can not carry out mold pressing with the method for routine.
The inventor finds that serving as a contrast the anti-leak pad in mould can prevent the seepage of natural graphite material effectively, thereby can make the negative material of the controllable thickness system with required form through big quantity research.
Anti-leak pad of the present invention is a kind of neutral material, with native graphite any reaction does not take place, and it has certain fineness, makes the product of mold pressing have smooth surface.And described anti-leak pad has certain resistance to wear, so that be repeatedly used.The examples of material that can be used as anti-leak pad of the present invention includes, but are not limited to pan paper, translucent drawing paper and copy paper.
One of the present invention preferably negative pole prepare in the example, earlier the native graphite of modification and electric conducting material and PVDF are mixed into uniform powder, drip subsequently till pyrrolidones to the PVDF powder of white disappears, upper and lower mould all be lined with the anti-leak pad mould in be molded into required thin cake.
The press that is used for mold pressing negative pole of the present invention can be conventional press, for example, can use the 769YP-15 type hydraulic press available from device High-tech company of Tianjin section.The pressure that uses during mold pressing is generally 0.2-15MPa.
Employed in the present invention electric conducting material can be an electric conducting material commonly used in this area, as acetylene black or graphite powder.
After making both positive and negative polarity, available conventional method is assembled into button cell with it.Fig. 1 is the profile of the button lithium ion battery of an example of the present invention.Among Fig. 1, label 1 is that negative cover, label 2 are that collector electrode, label 3 are that negative material, label 4 are that barrier film, label 5 are that positive cover, label 6 are that collector electrode, label 7 are that positive electrode, label 8 are packing rings.During manufacturing, to be placed on as the battery inner casing 1 of negative cover on the platform of press earlier, and will be pressed into the central authorities that the negative pole 3 that approaches round pie is placed on negative cover 1, electrolyte solution to negative pole cake 3 soaks into fully in the dropping, puts the plastic washer 8 of insulation usefulness subsequently on negative cover; Place barrier film 4 on the negative pole cake 3 and drip several electrolyte solutions; Then anodal cake 7 is overlayed on the barrier film 4, drip electrolyte to this positive pole cake 7 and soaked into fully; Add a cover the positive cover 5 of the conductive metal mesh that has welded; At last entire cell is placed press (the desk-top stamping machine of J04-16 type 16kN is available from captive shop of Shanghai Communications University) upper punch pressure seal mouth, form the button lithium rechargeable battery.
Those of ordinary skill in the art can easily calculate the thickness of anodal and negative pole in the button lithium rechargeable battery.For example, with the gross thickness control 1.8mm of both positive and negative polarity, the specific capacity of modified graphite is in 340mAh/g if desired, and the specific capacity of lithium-containing compound is in 130mAh/g, and then anodal and negative pole thickness separately can be estimated with following calculating formula:
x+y＝1.8
130×x×w
1＝340×y×w
2
X and y are respectively the thickness of anodal and negative material, w in the formula
1And w
2Be respectively the quality of the unit thickness of anodal and negative pole.The different thin cake of compacting is optimized back acquisition w by statistics under certain pressure
1And w
2Mean value:
| Project | Cake just as thin as a wafer | Negative pole approaches cake |
| The quality of unit thickness (mg/mm) | ????348 | ????182 |
| Pressure (N/mm 2) | ????150 | ????0.4 |
With the parameter that obtains respectively behind the substitution following formula, can calculate the thickness that the both positive and negative polarity cake is complementary and be respectively x=1.0-1.2mm, y=0.6-0.8mm.
The button lithium rechargeable battery that makes with the inventive method is under 1mA constant current charge-discharge condition, and discharge capacity can be up to 37mAh.Even at about 1mA/cm
2High current density, promptly under the 3mA constant current charge-discharge condition, discharge capacity also can reach 20mAh.After more than 40 constant current charge-discharge circulations, the capacity attenuation amount is less than 10%.Button lithium rechargeable battery of the present invention uses the native graphite of modification as negative material, because this material source is abundant, cheap and do not pollute the environment, thereby has greatly reduced production cost of cells of the present invention.
To further specify the present invention by embodiment below.
Embodiment
The method of testing of charge/discharge capacity:
Use BS-9300 type secondary cell device for detecting performance (available from intelligent instrument company of the electric research institute of GuangZhou, China) to record the capacity of battery with following method: to set charging voltage, make it to reach the magnitude of voltage of setting with the maximum that constant current I charges to voltage curve, write down the required charging interval, calculate charging capacity with following formula:
Charging capacity=charging interval (hour) * charging current (mA)
In like manner, when measuring the discharge capacity size, set greater than the discharge voltage value more than the 0V, be discharged to the magnitude of voltage that the minimum value of discharge curve equals to set with constant current value I and promptly accuse discharge off, the time that the record discharge is required, calculate discharge capacity in the same way.
Embodiment 1
Preparation is anodal
With the LiCoO of 85 weight portions available from German Merck company
2Powder, 10 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 5 weight portions PVDF powder available from Shanghai Organic fluoride research institute, dripping pyrrolidones to white subsequently while stirring disappears, the mixture that obtains is placed 10 minutes so that described mixture of powders swelling, be placed in the mould subsequently, in oil-hydraulic bench press (769YP-15 type, available from Tianjin section device high-tech company) in to be molded into diameter with the pressure of 15MPa be 16mm, the thin cake that 1.2mm is thick.With the thin cake that obtains at 120 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of Pa pressure.
The preparation negative pole
With 90 weight portions available from Xinghe, the Inner Mongol graphite ore and the modified graphite of the described method modification of disclosure patent application 97-326254 per diem, 5 weight portions evenly mix available from the acetylene black powder of Shanghai multiple elements chemical power supply factory and the 5 weight portions PVDF powder available from U.S. Ai Erfu atropic chemistry Shanghai office (Elfato China Shanghai), stirring change dropping pyrrolidones to white with the back disappears, the mixture that obtains is placed 15 minutes so that make described mixture of powders swelling, being placed on upper and lower mould subsequently all is lined with in the mould of pan paper, in oil-hydraulic bench press (769YP-15 type, available from Tianjin section device high-tech company) in to be molded into diameter with the pressure of 0.2MPa be 16mm, 0.61mm thick thin cake, with the thin cake that obtains at 120 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of Pa pressure.
Assemble
To be placed on the platform of the desk-top stamping machine of J04-16 type 16kN (available from captive shop of Shanghai Communications University) as the battery inner casing 1 of negative cover, and the above-mentioned negative pole 3 that is pressed into thin round pie is placed on the central authorities of negative cover 1, put the plastic washer 8 of insulation usefulness thereon, drip 15 1M LiPF subsequently
6/ EC+DMC (1: 1) electrolyte solution to negative pole cake 3 soaks into fully; Place Celgard 2400 polypropylene diaphragms 4 on the negative pole cake 3 and drip 4 electrolyte solutions; Then anodal cake 7 is overlayed on the barrier film 4, drip 15 described electrolyte to this positive pole cake 7 and soaked into fully; Add a cover the positive cover 5 of the conductive metal mesh that has welded; At last entire cell is placed press upper punch pressure seal mouth, form heavy 2.5g standard 2025 type button lithium rechargeable batteries.
The button cell that makes is tested charge/discharge capacity by top described method under the constant current conditions of 1mA, the results are shown in table 1.
Table 1
| Positive electrode | Charging capacity (mAh) for the first time | The 5th charging capacity (mAh) | Relative attenuation *???(％) | Discharge capacity (mAh) for the first time | The 5th discharge capacity (mAh) | Relative attenuation *???(％) |
| ??LiCoO 2 | ???41.8 | ???40.1 | ????4.2 | ????37 | ????36.8 | ????0.5 |
*Relative attenuation is that the amount of capacity with the 5th circulation time is that benchmark calculates.
As seen from the above table, after the 5th circulation, the capability retention of this chargeable button lithium ion battery is than higher, and capability retention surpasses 95% during charging, and capability retention is almost near 100% during discharge.Thereby the cycle performance that proves this battery is relatively good, and the chemical property of positive and negative pole material is more stable.
Fig. 2 is the voltage-time charging and discharging curve of this rechargeable type lithium ion battery under 1mA constant current charge-discharge condition.As seen from the figure, LiCoO
2The charge-discharge performance of the button cell of forming with modified natural graphite is better, and the basic symmetry of charging and discharging curve shows that lithium ion is in a basic balance from the embedding amount of taking off of both positive and negative polarity.
Embodiment 2
Preparation is anodal
With the LiCo of 80 weight portions available from Jingle Power Source Tech. Co., Ltd., Shanghai
0.5Ni
0.5O
2Powder, 11 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 9 weight portions PVDF powder available from U.S. Ai Erfu atropic chemistry Shanghai office, dripping pyrrolidones to white subsequently while stirring disappears, the mixture that obtains is placed 10 minutes so that described mixture of powders swelling, be placed in the mould subsequently, being molded into diameter with the pressure of 10MPa in 769YP-15 type oil-hydraulic bench press is 16mm, the thin cake that 1.0mm is thick.With the thin cake that obtains at 120 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of handkerchief pressure.
The preparation negative pole
With 82 weight portions available from Shandong, Hunan pool graphite ore and use modified graphite with embodiment 1 same procedure modification, 10 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 8 weight portions PVDF powder available from U.S. Ai Erfu atropic chemistry Shanghai office, stirring change dropping pyrrolidones to white with the back disappears, the mixture that obtains is placed 12 minutes so that make described mixture of powders swelling, being placed on upper and lower mould subsequently all is lined with in the mould of translucent drawing paper, being molded into diameter with the pressure of 10MPa in 769YP-15 type oil-hydraulic bench press is 16mm, 0.8mm thick thin cake, with the thin cake that obtains at 130 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of Pa.
Assemble
With the method identical with embodiment 1, but with 1M LiPF
6/ EC+DEC (1: 1) electrolyte solution is as electrolyte, with positive pole that makes above and negative pole assembling button lithium rechargeable battery.
The button cell that makes is tested charge/discharge capacity by top described method under the 1mA constant current conditions, the results are shown in table 2.
Table 2
| Positive electrode | Charging capacity (mAh) for the first time | The 5th charging capacity (mAh) | Relative attenuation *???(％) | Discharge capacity (mAh) for the first time | The 5th discharge capacity (mAh) | Relative attenuation *???(％) |
| LiCo 0.5Ni 0.5O 2 | ????32 | ????29.5 | ????8.4 | ????28 | ????27.9 | ????0.3 |
*Relative attenuation is that the amount of capacity with the 5th circulation time is that benchmark calculates.
The charging and discharging curve of this battery as shown in Figure 3.
Preparation is anodal
With the LiMn of 90 weight portions available from German Merck company
2O
4Powder, 5 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 5 weight portions PVDF powder available from Shanghai Organic fluoride research institute, dripping pyrrolidones to white subsequently while stirring disappears, the mixture that obtains is placed 14 minutes so that described mixture of powders swelling, be placed in the mould subsequently, being molded into diameter with the pressure of 5MPa in 769YP-15 type bench press is 16mm, the thin cake that 1.0mm is thick.With the thin cake that obtains at 130 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of handkerchief.
The preparation negative pole
The modified graphite that 88 weight portions and embodiment 2 is identical, 7 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 5 weight portions PVDF powder available from Shanghai Organic fluoride research institute, stirring change dropping pyrrolidones to white with the back disappears, the mixture that obtains is placed 12 minutes so that make described mixture of powders swelling, being placed on upper and lower mould subsequently all is lined with in the mould of copy paper, being molded into diameter with the pressure of 15MPa in 769YP-15 type bench press is 16mm, 0.8mm thick thin cake, with the thin cake that obtains at 130 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of Pa.
Assemble
With the method identical with embodiment 1, but with 1M LiPF
6/ EC+DEC (1: 1) electrolyte solution is as electrolyte, with positive pole that makes above and negative pole assembling button lithium rechargeable battery.
The button cell that makes is tested charge/discharge capacity by top described method under the 1mA constant current conditions, the results are shown in table 3.
Table 3
| Positive electrode | Charging capacity (mAh) for the first time | The 5th charging capacity (mAh) | Relative attenuation *????(％) | Discharge capacity (mAh) for the first time | The 5th discharge capacity (mAh) | Relative attenuation *???(％) |
| ??LiMn 2O 4 | ????22 | ????21.6 | ????1.8 | ????20 | ?????19.9 | ????0.5 |
*Relative attenuation is that the amount of capacity with the 5th circulation time is that benchmark calculates.
The charging and discharging curve of this battery as shown in Figure 4.
Embodiment 4
Preparation is anodal
With the LiCoO of 82 weight portions available from Jingle Power Source Tech. Co., Ltd., Shanghai
2Powder, 8 weight portions evenly mix available from the acetylene black powder of carbon element factory, Shanghai and the 10 weight portions PVDF powder available from U.S. Ai Erfu atropic chemistry Shanghai office, dripping pyrrolidones to white subsequently while stirring disappears, the mixture that obtains is placed 10 minutes so that described mixture of powders swelling, be placed in the mould subsequently, being molded into diameter with the pressure of 25MPa in 769YP-15 type oil-hydraulic bench press is 16mm, the thin cake that 1.3mm is thick.With the thin cake that obtains at 130 ℃, 10
5Oven dry is stand-by in the vacuum drying oven of handkerchief.
The preparation negative pole
The modified graphite that 92 weight portions and embodiment 1 is identical, 4 weight portions evenly mix available from the acetylene black powder of Shanghai multiple elements chemical power supply factory and the 4 weight portions PVDF powder available from U.S. Ai Erfu atropic chemistry Shanghai office, stirring change dropping pyrrolidones to white with the back disappears, the mixture that obtains is placed 10 minutes so that make described mixture of powders swelling, being placed on upper and lower mould subsequently all is lined with in the mould of translucent drawing paper, being molded into diameter with the pressure of 2MPa in the 769YP-15 oil-hydraulic bench press is 16mm, 0.55mm thick thin cake, with the thin cake that obtains at 130 ℃, oven dry is stand-by in the vacuum drying oven of 105Pa.
Assemble
With the method identical with embodiment 1, but with 1M LiPF
6/ EC+DEC (1: 1) electrolyte solution is as electrolyte, with positive pole that makes above and negative pole assembling button lithium rechargeable battery.The battery that makes is at room temperature carried out the test of charge/discharge capacity through 1-3mA constant current charge-discharge condition.Fig. 5 is that this battery is in the variation of the 5th circulation time capacity with electric current; Capacity under big current condition after more than 40 circulations is shown in Fig. 6.As seen from Figure 6, even (density of charging current has reached 1mA/cm under 3mA constant current charge-discharge condition
2About) discharge capacity is still up to more than the 20mAh, after more than 40 times big electric current constant current charge-discharge circulation, capacity only decays about 10% simultaneously.Show that button lithium rechargeable battery of the present invention has high capacity and stable chemical property.
Embodiment 5
Prepare lithium ion battery with the method identical, but use 87 weight portion LiCoO when anodal making with embodiment 4
2Powder, 9 weight portion acetylene black powder and 4 weight portion PVDF, the pressure of mold pressing is 20MPa.It is similar that the performance of the button lithium ion battery that makes and embodiment 4 make.
Although describe the present invention in conjunction with non-restrictive example, those of ordinary skill in the art can easily carry out various changes and modifications to the present invention under the precursor that does not depart from spirit of the present invention.Therefore, scope of the present invention is limited by the accompanying claims.
Claims (10)
1. button lithium rechargeable battery, it comprises lithium-containing compound positive pole, graphite cathode and barrier film, it is characterized in that the anodal and graphite cathode of described lithium-containing compound all is compression moldings.
2. battery as claimed in claim 1 is characterized in that described lithium-containing compound is selected from LiMn
2O
4, LiCoO
2Or LiNi
1-xCo
xO
2, 0.2≤x≤1 wherein.
3. battery as claimed in claim 1 or 2 is characterized in that the total weight by positive electrode, and described lithium-containing compound positive pole contains 80-90 weight % lithium-containing compound, contains 5-11 weight % electric conducting material, contains 4-10 weight %PVDF.
4. battery as claimed in claim 3 is characterized in that the total weight by positive electrode, and described lithium-containing compound positive pole contains 85 weight % lithium-containing compounds, contains 10 weight % electric conducting materials, contains 5 weight %PVDF.
5. battery as claimed in claim 1 or 2 is characterized in that the total weight by negative material, and described graphite cathode contains 82-92 weight % modified natural graphite, contains 4-10 weight % electric conducting material, contains 4-8 weight %PVDF.
6. battery as claimed in claim 5 is characterized in that the total weight by negative material, and described graphite cathode contains 90 weight % modified natural graphites, contains 5 weight % electric conducting materials, contains 5 weight %PVDF.
7. the preparation method of a button lithium rechargeable battery, it comprises
1) forms the lithium-containing compound positive pole;
2) form graphite cathode;
3) anodal and described graphite cathode and barrier film are assembled into the button lithium rechargeable battery with described lithium-containing compound;
It is characterized in that described lithium-containing compound positive pole and graphite cathode all are compression moldings.
8. method as claimed in claim 7 is characterized in that when compression molding, and lining is gone into the anti-leak pad in mould.
9. method as claimed in claim 8 is characterized in that described anti-leak pad is selected from pan paper, translucent drawing paper or copy paper.
10. as any one described method among the claim 7-9, the molding pressure that it is characterized in that described lithium-containing compound positive pole is 5-25MPa, and the molding pressure of described graphite cathode is 0.2-15MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113712A CN1274179A (en) | 1999-05-17 | 1999-05-17 | Button-type secondary lithium ion battery and its manufacture technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113712A CN1274179A (en) | 1999-05-17 | 1999-05-17 | Button-type secondary lithium ion battery and its manufacture technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1274179A true CN1274179A (en) | 2000-11-22 |
Family
ID=5276873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113712A Pending CN1274179A (en) | 1999-05-17 | 1999-05-17 | Button-type secondary lithium ion battery and its manufacture technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274179A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7858232B2 (en) | 2004-11-15 | 2010-12-28 | Panasonic Corporation | Non-aqueous electrolyte secondary battery |
| CN108346779A (en) * | 2017-01-25 | 2018-07-31 | 武汉理工力强能源有限公司 | A kind of preparation method of the lithium metal battery with ultra high energy density |
-
1999
- 1999-05-17 CN CN99113712A patent/CN1274179A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7858232B2 (en) | 2004-11-15 | 2010-12-28 | Panasonic Corporation | Non-aqueous electrolyte secondary battery |
| US7955735B2 (en) | 2004-11-15 | 2011-06-07 | Panasonic Corporation | Non-aqueous electrolyte secondary battery |
| CN108346779A (en) * | 2017-01-25 | 2018-07-31 | 武汉理工力强能源有限公司 | A kind of preparation method of the lithium metal battery with ultra high energy density |
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