CN105591102A - High-safety long-cycle life lithium iron phosphate polymer lithium ion energy storage battery - Google Patents
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a high-safety long-cycle life lithium iron phosphate polymer lithium ion energy storage battery. The battery adopts the laminating mode that cathode plates and anode plates are alternately laminated in a Z shape, and the cathode plates and the anode plates are separated by diaphragms. The lithium iron phosphate polymer lithium ion energy storage battery has the ultralong cycle life (the 1-C cycle life is longer than or equal to 2000 times, and 80% of the maximum capacity of the first 5 weeks serves as a cycle end) and the good safety performance (both needling and circuit shorting cannot cause a fire, exploding and smoking).
Description
Technical field
The present invention relates to polymer Li-ion battery, particularly a kind of lithium iron phosphate polymer lithium ion energy-storage battery of high safe long circulation life.
Background technology
Clean energy resource industry has the excellent attributes such as green, environmental protection, sustainable development, is the new industry that state key advances, and is the important directions of China's Economic Transition. New forms of energy are the mainstay of the industrial revolution for the third time as the representative of clean energy resource, and the build-in attribute of cylinder (box hat) lithium ion battery has limited its application on large electric appliances equipment, power vehicle, the short course continuation mileage that limits automobile of cycle life, increase cost investment, limited the development of this industry. The lithium iron phosphate polymer lithium ion battery that the present invention proposes has the cycle life of overlength and good security performance, ensure greatly to have improved safe time the flying power of electric automobile, for the application of lithium ion battery on electric automobile provides technical guarantee.
Summary of the invention
The invention discloses lithium iron phosphate polymer lithium ion energy-storage battery of a kind of high security long circulation life and preparation method thereof, be to overcome the shortcomings such as short, poor safety performance in the service life of lithium ion battery applications on electric automobile.
For overcoming above-mentioned shortcoming, the present invention by the following technical solutions:
A kind of lithium iron phosphate polymer lithium ion energy-storage battery of high safe long circulation life, it is characterized in that, the component of described anode sizing agent and percentage by weight (wt%) are: 93.8% LiFePO4,2.0% conductive agent conductive carbon black, 1.0% conductive agent electrically conductive graphite, 3.2% binding agent Kynoar; Plus plate current-collecting body adopts aluminium foil.
A kind of lithium iron phosphate polymer lithium ion energy-storage battery of high safe long circulation life, it is characterized in that, the component of described cathode size and percentage by weight (wt%) are: 94.7% Delanium, 1.0% conductive agent conductive carbon black, 1.6% thickener sodium carboxymethylcellulose, 2.7% binding agent butadiene-styrene rubber, the addition of 1-METHYLPYRROLIDONE is 10% of butadiene-styrene rubber quality; Negative current collector adopts Copper Foil.
A lithium iron phosphate polymer lithium ion energy-storage battery for high safe long circulation life, is characterized in that, is prepared by following steps:
(1) Kynoar is joined in 1-METHYLPYRROLIDONE to logical circulating water vacuum stirring 3h; The glue vacuum preparing adds conductive carbon black and electrically conductive graphite after leaving standstill 3-4h, stirs 3h; Finally add LiFePO4 powder, stir 4h, the slurry obtaining is crossed 150 mesh sieve 1 time;
(2) sodium carboxymethylcellulose is added in a certain amount of deionized water to logical circulating water vacuum stirring 2h; The glue vacuum preparing adds conductive carbon black after leaving standstill 3-4h, stirs 2h; Then add Delanium to stir 3h; Finally add butadiene-styrene rubber and 1-METHYLPYRROLIDONE to stir 1h, slurry is crossed 150 mesh sieve 1 time after 0.5h froth breaking;
(3) anodal coating used thickness is the aluminium foil of 16 μ m, and negative pole coating used thickness is the Copper Foil of 10 μ m;
(4) both positive and negative polarity after coating twists in 105 DEG C of baking 12h in air blast baking box, and every 2h charges and discharge nitrogen one time;
(5) roll-in positive/negative plate, carries out cross cutting by pole piece good roll-in, requires to select suitable cutting die according to battery size;
(6) require to take " Z " font positive plate, negative plate to replace lamination according to battery design, the membrane thicknesses of described battery is 20 μ m;
(7) require positive and negative electrode lug ultra-sonic welded to be fixed on both positive and negative polarity lug position according to battery design, on lug, leave fibrous encapsulation glue;
(8) the qualified battery core that is soldered lug is put into made aluminum plastic film housing, carry out top side seal;
(9) the 80 DEG C of vacuum bakeout 48h in vacuum oven of the battery core after top side seal, every 1h charges and discharge nitrogen one time, and the battery core after baking is injected electrolyte in the environment of dew point≤-50 DEG C, proceeds to high hot house tiling and shelve 48h after the side of Vacuum Package gasbag;
(10) battery changes into: adopt high-temperature pressurizing to change into, chemical synthesis technology is 0.02C constant-current charge 0.5h, 0.05C constant-current charge 4h, and 0.2C constant-current charge 4h, wherein changing into temperature is 45 DEG C; Changing into pressure is 2kgf/cm2；
(11) will after the battery normal temperature shelf 24-36h after changing into, carry out secondary encapsulation, cut the boiling hot shaping of folding;
(12) battery partial volume: partial volume technique is for leaving standstill 5min; 0.5C constant-current constant-voltage charging is to 3.65V, cut-off current 0.02C; Leave standstill 5min; 0.5C constant-current discharge is to 2.5V; Leave standstill 5min; 0.5C constant-current constant-voltage charging is to 3.65V, cut-off current 0.02C.
The described anodal coated face density of step (3) is 260g/m2, described negative pole coated face density is 124g/m2。
The described electrolyte model of step (9) is LB4501G.
The battery that the present invention produces has the cycle life of overlength and good security performance, effectively widen the application of lithium ion polymer battery in electric automobile field, under the prerequisite that ensures installation and use procedure safety, effectively improved the flying power of electric automobile.
Detailed description of the invention
Battery acupuncture experiment test standard: battery 0.5C is full of to electricity, with the high temperature resistant draw point of φ 3mm-φ 8mm, with the speed of 10mm/s-40mm/s, runs through (draw point rests on 1min battery) from the direction perpendicular to battery pole plates;
Battery short circuit experiment test standard: 0.5C is full of to electric battery through external short circuit 10min, and outside line resistance is answered < 5m Ω.
Embodiment 1
A kind of lithium iron phosphate polymer lithium ion energy-storage battery, comprises positive plate, negative plate, barrier film, electrolyte, positive and negative electrode lug, aluminum plastic film housing that 20 μ m are thick. Wherein positive pole is made up of positive active material, binding agent, conductive agent and plus plate current-collecting body, and anode sizing agent proportioning is: positive active material adopts the LiFePO4 powder of 93.8wt%; Binding agent adopts the Kynoar of 3.2wt%; Conductive agent adopts the conductive carbon black of 2.0wt% and the electrically conductive graphite of 1.0wt%; Plus plate current-collecting body adopts the thick aluminium foil of 16 μ m; Negative pole is made up of negative material, conductive agent, thickener, binding agent and negative current collector, and cathode size proportioning is: negative material adopts the Delanium of 94.7wt%; Conductive agent adopts the conductive carbon black of 1.0wt%; Thickener adopts the sodium carboxymethylcellulose of 1.6wt%; Binding agent adopts the butadiene-styrene rubber of 2.7wt%; The addition of 1-METHYLPYRROLIDONE is 1/10 of butadiene-styrene rubber quality, in order to prevent crisp of pole piece; Negative current collector adopts the thick Copper Foil of 10 μ m.
The manufacture craft of lithium iron phosphate polymer lithium ion energy-storage battery is as follows:
(1) Kynoar of 0.341kg is joined in the 1-METHYLPYRROLIDONE of 13.029kg to logical circulating water vacuum stirring 3h; The glue vacuum preparing adds the conductive carbon black of 0.213kg and the electrically conductive graphite of 0.106kg after leaving standstill 3-4h, stirs 3h; Finally add 10kg LiFePO4 powder, stir 4h, the slurry obtaining is crossed 150 mesh sieve 1 time;
(2) 0.096kg sodium carboxymethylcellulose is added in a certain amount of deionized water to logical circulating water vacuum stirring 2h; The conductive carbon black that adds 0.06kg after the standing 3-4h of glue vacuum preparing, stirs 2h; Then add the Delanium of 5.682kg to stir 3h; Finally add butadiene-styrene rubber and the 1-METHYLPYRROLIDONE of 0.324kg to stir 1h, slurry is crossed 150 mesh sieve 1 time after 0.5h froth breaking;
(3) anodal coating used thickness is the aluminium foil of 16 μ m, and negative pole coating used thickness is the Copper Foil of 10 μ m;
(4) both positive and negative polarity after coating twists in 105 DEG C of baking 12h in air blast baking box, and every 2h charges and discharge nitrogen one time;
(5) roll-in positive/negative plate, carries out cross cutting by pole piece good roll-in, and pole piece is of a size of: (long * is wide for positive plate
=180*133mm), negative plate (long * wide=184*136mm);
(6) require to take " Z " font positive plate, negative plate to replace lamination according to battery design, the membrane thicknesses of battery is 20 μ m; Anodal 25,26, negative pole;
(7) require positive and negative electrode lug ultra-sonic welded to be fixed on both positive and negative polarity lug position according to battery design, on lug, leave fibrous encapsulation glue;
(8) the qualified battery core that is soldered lug is put into made aluminum plastic film housing, carry out top side seal;
(9) the 80 DEG C of vacuum bakeout 48h in vacuum oven of the battery core after top side seal, every 1h charges and discharge nitrogen one time,
Battery core after baking is injected 100g electrolyte in the environment of dew point≤-50 DEG C, and electrolyte model is respectively LB4501G, proceeds to high hot house tiling and shelve 48h after the side of Vacuum Package gasbag;
(10) battery changes into: adopt high-temperature pressurizing to change into, chemical synthesis technology is 0.02C constant-current charge 0.5h, 0.05C
Constant-current charge 4h, 0.2C constant-current charge 4h, wherein changing into temperature is 45 DEG C; Changing into pressure is 2kgf/cm2；
(11) will after the battery normal temperature shelf 24-36h after changing into, carry out secondary encapsulation, cut the boiling hot shaping of folding;
(12) battery partial volume: partial volume technique is for leaving standstill 5min; 0.5C constant-current constant-voltage charging is to 3.65V, and cut-off is electric
Stream 0.02C; Leave standstill 5min; 0.5C constant-current discharge is to 2.5V; Leave standstill 5min; 0.5C constant-current constant-voltage charging
To 3.65V, cut-off current 0.02C; The battery size obtaining is that 90140200-20Ah-3.2V LiFePO4 is poly-
Compound lithium ion battery (wherein cell thickness is 9mm, and width is 140mm, and length is 200mm).
Embodiment 2 to 3
Identical with the manufacture craft major part in embodiment 1, difference is the electrolyte model difference that fluid injection operation is used, and the model of the lithium-ion energy storage battery electrolyte used of making in the embodiment of the present invention and quality are as shown in Table 1.
Table one
The performance comparison of the lithium-ion-power cell that embodiment makes as shown in Table 2.
Table two
The lithium-ion energy storage battery 1C cyclic curve figure (cycle-index-discharge capacity) making in the embodiment of the present invention as shown in Figure 1, under the identical prerequisite of reservoir quantity, make electrolyte into SWHT-B001 and TC-E8022 by LB4501G, the not too large variation of gravimetric specific energy, energy density per unit volume and the security performance of battery, but decay in various degree appears in cycle life, illustrate that the cycle performance of battery is performed to optimum state by the electrolyte of LB4501G model.
Claims (5)
1. the lithium iron phosphate polymer lithium ion energy-storage battery of a high safe long circulation life, it is characterized in that, the component of described anode sizing agent and percentage by weight (wt%) are: 93.8% LiFePO4,2.0% conductive agent conductive carbon black, 1.0% conductive agent electrically conductive graphite, 3.2% binding agent Kynoar; Plus plate current-collecting body adopts aluminium foil.
2. the lithium iron phosphate polymer lithium ion energy-storage battery of a high safe long circulation life, it is characterized in that, the component of described cathode size and percentage by weight (wt%) are: 94.7% Delanium, 1.0% conductive agent conductive carbon black, 1.6% thickener sodium carboxymethylcellulose, 2.7% binding agent butadiene-styrene rubber, the addition of 1-METHYLPYRROLIDONE is 10% of butadiene-styrene rubber quality; Negative current collector adopts Copper Foil.
3. a lithium iron phosphate polymer lithium ion energy-storage battery for high safe long circulation life, is characterized in that, is prepared by following steps:
(1) Kynoar is joined in 1-METHYLPYRROLIDONE to logical circulating water vacuum stirring 3h; The glue vacuum preparing adds conductive carbon black and electrically conductive graphite after leaving standstill 3-4h, stirs 3h; Finally add LiFePO4 powder, stir 4h, the slurry obtaining is crossed 150 mesh sieve 1 time;
(2) sodium carboxymethylcellulose is added in a certain amount of deionized water to logical circulating water vacuum stirring 2h; The glue vacuum preparing adds conductive carbon black after leaving standstill 3-4h, stirs 2h; Then add Delanium to stir 3h; Finally add butadiene-styrene rubber and 1-METHYLPYRROLIDONE to stir 1h, slurry is crossed 150 mesh sieve 1 time after 0.5h froth breaking;
(3) anodal coating used thickness is the aluminium foil of 16 μ m, and negative pole coating used thickness is the Copper Foil of 10 μ m;
(4) both positive and negative polarity after coating twists in 105 DEG C of baking 12h in air blast baking box, and every 2h charges and discharge nitrogen one time;
(5) roll-in positive/negative plate, carries out cross cutting by pole piece good roll-in, requires to select suitable cutting die according to battery size;
(6) require to take " Z " font positive plate, negative plate to replace lamination according to battery design, the membrane thicknesses of described battery is 20 μ m;
(7) require positive and negative electrode lug ultra-sonic welded to be fixed on both positive and negative polarity lug position according to battery design, on lug, leave fibrous encapsulation glue;
(8) the qualified battery core that is soldered lug is put into made aluminum plastic film housing, carry out top side seal;
(9) the 80 DEG C of vacuum bakeout 48h in vacuum oven of the battery core after top side seal, every 1h charges and discharge nitrogen one time, and the battery core after baking is injected electrolyte in the environment of dew point≤-50 DEG C, proceeds to high hot house tiling and shelve 48h after the side of Vacuum Package gasbag;
(10) battery changes into: adopt high-temperature pressurizing to change into, chemical synthesis technology is 0.02C constant-current charge 0.5h, 0.05C constant-current charge 4h, and 0.2C constant-current charge 4h, wherein changing into temperature is 45 DEG C; Changing into pressure is 2kgf/cm2；
(11) will after the battery normal temperature shelf 24-36h after changing into, carry out secondary encapsulation, cut the boiling hot shaping of folding;
(12) battery partial volume: partial volume technique is for leaving standstill 5min; 0.5C constant-current constant-voltage charging is to 3.65V, cut-off current 0.02C; Leave standstill 5min; 0.5C constant-current discharge is to 2.5V; Leave standstill 5min; 0.5C constant-current constant-voltage charging is to 3.65V, cut-off current 0.02C.
4. according to the lithium iron phosphate polymer lithium ion energy-storage battery of a kind of high safe long circulation life described in claims 3, it is characterized in that, the described anodal coated face density of step (3) is 260g/m2, described negative pole coated face density is 124g/m2。
5. according to the lithium iron phosphate polymer lithium ion energy-storage battery of a kind of high safe long circulation life described in claims 3, it is characterized in that, the described electrolyte model of step (9) is LB4501G.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111342161A (en) * | 2020-04-08 | 2020-06-26 | 河南华瑞高新材料有限公司 | Rapid formation and grading method for soft package battery using high-nickel electrolyte |
| CN111446504A (en) * | 2020-04-02 | 2020-07-24 | 新乡华锐锂电新能源有限公司 | Rapid formation and grading method for soft package battery using high-voltage electrolyte |
| CN111551572A (en) * | 2020-05-21 | 2020-08-18 | 安徽科达新材料有限公司 | Method for rapidly evaluating cycle performance of graphite material in battery |
| CN113140818A (en) * | 2021-02-27 | 2021-07-20 | 浙江锋锂新能源科技有限公司 | Lithium metal battery pretreatment process and lithium metal battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101183729A (en) * | 2007-12-14 | 2008-05-21 | 山东海霸通讯设备有限公司 | High capacity lithium iron phosphate power cell and production technique thereof |
| CN101409369A (en) * | 2008-11-14 | 2009-04-15 | 东莞市迈科科技有限公司 | Large-capacity high power polymer ferric lithium phosphate power cell and preparation method thereof |
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2015
- 2015-12-17 CN CN201510951979.5A patent/CN105591102A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101183729A (en) * | 2007-12-14 | 2008-05-21 | 山东海霸通讯设备有限公司 | High capacity lithium iron phosphate power cell and production technique thereof |
| CN101409369A (en) * | 2008-11-14 | 2009-04-15 | 东莞市迈科科技有限公司 | Large-capacity high power polymer ferric lithium phosphate power cell and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111446504A (en) * | 2020-04-02 | 2020-07-24 | 新乡华锐锂电新能源有限公司 | Rapid formation and grading method for soft package battery using high-voltage electrolyte |
| CN111342161A (en) * | 2020-04-08 | 2020-06-26 | 河南华瑞高新材料有限公司 | Rapid formation and grading method for soft package battery using high-nickel electrolyte |
| CN111551572A (en) * | 2020-05-21 | 2020-08-18 | 安徽科达新材料有限公司 | Method for rapidly evaluating cycle performance of graphite material in battery |
| CN111551572B (en) * | 2020-05-21 | 2023-02-03 | 安徽科达新材料有限公司 | Method for rapidly evaluating cycle performance of graphite material in battery |
| CN113140818A (en) * | 2021-02-27 | 2021-07-20 | 浙江锋锂新能源科技有限公司 | Lithium metal battery pretreatment process and lithium metal battery |
| CN113140818B (en) * | 2021-02-27 | 2022-09-06 | 浙江锋锂新能源科技有限公司 | Lithium metal battery pretreatment process and lithium metal battery |
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Application publication date: 20160518 |