CN102201605A - Electrochemical energy storage and conversion device having bipolar structure - Google Patents
Electrochemical energy storage and conversion device having bipolar structure Download PDFInfo
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- CN102201605A CN102201605A CN2010101293622A CN201010129362A CN102201605A CN 102201605 A CN102201605 A CN 102201605A CN 2010101293622 A CN2010101293622 A CN 2010101293622A CN 201010129362 A CN201010129362 A CN 201010129362A CN 102201605 A CN102201605 A CN 102201605A
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to an electrochemical energy storage and conversion device having a bipolar structure. The electrochemical energy storage and conversion device comprises a bipolar electrode, a diaphragm and a nonaqueous electrolytic solution, wherein one side of the bipolar electrode current collector is made of a positive electrode active material of a lithium battery, and the other side of the bipolar electrode current collector is made of a negative electrode material of a capacitor. As the negative electrode of the electrochemical energy storage and conversion device adopts a combination of lithium titanate and active carbon, the lithium titanate is a lithium-embedded active material, and overcharged electric quantity can be absorbed by the active carbon in a double-electric-layer capacitance/lithium absorption manner; and the electrochemical energy storage and conversion device has the characteristic of large current density working; meanwhile, under overcharging, the lithium ion can be absorbed into a micropore of the active carbon, so the safety influence on the electrochemical device due to separation of the active metal lithium can be avoided; and the electrochemical energy storage and conversion device has the advantages of adjustable voltage, high energy, high specific power, high safety, long service life and the like.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly relate to a kind of electrochemical energy storage and energy conversion device with bipolar structure.
Background technology
At present, lithium ion battery with its superior chemical property and environment friendly and be widely used in mobile phone, computer, take the photograph/video tape recorder, field such as electric tool, motor vehicle; Electrochemical capacitor is with its high power and long-life characteristics and be widely used in back-up source (UPS), the pulse power, peak load regulation network, startup power supply and hybrid vehicle etc.The positive electrode employing cobalt acid lithium of general middle-size and small-size lithium ion battery etc. has the transition metal oxide of layer structure, the positive electrode of power lithium-ion battery adopts higher spinel lithium manganate or the olivine LiFePO4 of fail safe, and negative material adopts native graphite, electrographite and coke class material with carbon element more.But there are serious problems in fail safe and operating mode in lithium ion battery on the life-span, and there is the problem of specific energy deficiency in electrochemical capacitor.Lithium titanate has higher current potential (1.5Vvs.Li/Li with respect to carbon class material as the zero strain material in addition
+), and demonstrating long-life and safe feature, it is considered to good power battery cathode material and capacitor material.Lithium ion battery and the lithium-ion capacitor that electrochemical capacitor is compounded to form have that power-performance is good, the characteristics of the relative higher and safety long-life of specific energy, are subjected to extensive concern.In addition, traditional lithium ion battery and electrochemical capacitor adopt coiling or lamination to make monomer, and voltage is lower, be generally 2.5-5V as lithium ion battery voltage, electrochemical capacitor of organic system voltage is generally 2.7-3.2V, need connect monomer poor reliability for realizing high voltage.
Invention CN1710744A discloses a kind of preparation method of nano cell, it is characterized in that the anodal cobalt acid lithium that adopts, and negative pole adopts nano lithium titanate to prepare the colloid lithium ion battery, and its main purpose is to reduce cost.
Invention CN101110477 discloses a kind of electrochemical energy storage device, it is characterized in that the anodal lithium ion battery material-ternary material that adopts, negative pole adopts the mixture of lithium titanate and active carbon, realize a kind of hybrid accumulator, adopt traditional lamination, provide a kind of low voltage electrochemical energy storage device.
Invention CN1985400 discloses a kind of bipolar electrode battery pack, it is characterized in that adopting the collector of high polymer material.This invention remains the lithium ion battery of traditional concept.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of interior combined type electrochemical energy storage and energy conversion device of bipolar structure is provided, this device has characteristics such as voltage is adjustable, safe and reliable, specific energy is high, the life-span is long.
Electrochemical energy storage of the present invention and energy conversion device adopt following technical scheme:
A kind of electrochemical energy storage and energy conversion device with bipolar structure, comprise bipolar electrode, barrier film and nonaqueous electrolyte, it is characterized in that: a side of described bipolar electrode collector is an anode active material of lithium ion battery, contains the lithium ion transistion metal compound that can absorb/emit lithium ion; Opposite side is a capacitor anode material, contains oxidation-reduction potential and is higher than the lithium ion battery active material of 1.0V vs.Li/Li+ and the mixture or the compound of activated carbon.
And described anode active material of lithium ion battery is Li (NiCoMn) O
2
And described capacitor anode material is the mixture/compound of lithium titanate and activated carbon.
And described collector is an aluminum foil current collector.
And described barrier film is the colloidal electrolyte film.
Advantage that the present invention has and good effect:
1, negative pole of the present invention adopts the combination of lithium titanate and activated carbon, can guarantee the active material of lithium titanate as the embedding lithium, can be absorbed the electric weight that overcharges by the form of activated carbon with electric double layer capacitance/lithium absorption again, but have the characteristic of high current density work; Simultaneously, lithium ion can be adsorbed in the activated carbon capillary when overcharging, and can not cause separating out of reactive metal lithium and influences the safety problem of this electrochemical energy storage device, has advantages such as voltage is adjustable, energy is high, specific power is big, fail safe is good, the life-span is long.
2, the present invention adopts Li (NiCoMn) O of height ratio capacity
2, negative pole employing lithium titanate mixes/compound with activated carbon, has Li (NiCoMn) O of layer structure
2Positive electrode not only capacity is big, and can also keep good invertibity when high potential (4.8V vs.Li/Li+), and the exothermic reaction temperature is lower than the sour lithium of cobalt, has good safety performance.Oxidation-reduction potential height of novel negative material lithium titanate (1.5V vs.Li/Li+) and the change in volume when discharging and recharging are little, are desirable long circulation life materials, also are applied to the asymmetric capacitor field simultaneously.
Description of drawings
Fig. 1 is electrochemical energy storage and the energy conversion device electricity core schematic diagram with bipolar structure of the present invention;
Fig. 2 is the have electrochemical energy storage of bipolar structure and the charging and discharging curve of energy conversion device of the present invention;
Wherein, 1-lithium ion cell positive, 2-mixing/composite negative pole, 3-collector, 4-barrier film, 5-lug.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and by specific embodiment, and following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
The LiNi that the present invention enumerates
1/3Co
1/3Mn
1/3O
2Positive electrode active materials, it also can be the lithium transition-metal oxide lamellar compound of Mn content other components of being no more than transition metal molar content 1/2, but with the component of high Mn low Ni, Co for well, but also doped with Al, Mg, or the positive pole of the compound of the molar content of Li between 1-1.2; Positive pole also can be LiMn with lithium-containing compound simultaneously
2O
4, LiMPO
4(M:Fe, Mn, V) etc.
Embodiment 1: with reference to accompanying drawing 1, Fig. 2.
A kind of electrochemical energy storage and energy conversion device with bipolar structure, comprise bipolar electrode, barrier film 4 and nonaqueous electrolytic solution, wherein, bipolar electrode is made of the negative pole that comprises lithium titanate and Mixture of Activated Carbon/compound 2 of aluminum foil current collector 3 with anodal coating 1 of the nickel cobaltous manganese lithium oxide active material that comprises layer structure that is coated in the one side and opposite side.
1. the making of double polarity plate
Take by weighing the D50 particle diameter and be 8 microns LiNi
1/3Co
1/3Mn
1/3O
2(ternary) positive electrode active materials, adhesive and conductive agent, by N-N-methyl-2-2-pyrrolidone N-(NMP) solution of the positive electrode active materials mixture of 93wt%, polyvinylidene fluoride (PVdF) bonding agent and to make the content of PVdF be 4.5wt%, as the 2.5wt% acetylene black of electric conducting material, mix and form cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably the single face that thickness is 20 μ m aluminium foils, dried coating weight is 8mg/cm2.
The active carbon of 16.8% (weight), the average particle crystalline substance of 67.2% (weight) is the Li of 300 nanometers
4Ti
5O
12The PVdF of the VGCF of 1% (weight), 2% acetylene black and 13% (weight) (the solution mode with NMP adds) makes pastel, then this pastel is coated onto equably the another side (not being coated with the material side) of above-mentioned aluminium foil, drying again, coating weight is 12mg/cm2.Roll-in and make double polarity plate then.
Be about 50 microns the Al that is mixed with thickness
2O
3Aerocolloidal PVdF perforated membrane is made diaphragm body, fully soaks into electrolyte before using and makes it swelling.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6The mixed solvent solution of EC+DEC+DMC (volume ratio 1: 1: 1).
2. the assembling that has the electrochemical energy storage and the energy conversion device of bipolar structure
Above-mentioned bipolar plates, barrier film are stacked at interval, guarantee that positive and negative pole-face is relative through barrier film, the outermost electrode is respectively the single face positive pole and negative pole forms electric core, weld lug 5, after 70oC vacuumize electric core is inserted in the plastic-aluminum combined Soft Roll encapsulation, fluid infusion is to not having the electrolyte of flowing, vacuum seal again.Positive and negative very three pairs of present embodiment so are assembled into flexible-packed battery as battery A1, and Fig. 1 is the structural representation of the electric core of electrochemical energy storage with bipolar structure of the present invention and energy converter device, and carries out electro-chemical test as follows.
3. charge-discharge test
At first carried out volume test.Be charged as CC (constant current) pattern; Discharge is all CC (constant current) pattern.Promptly use 1C multiplying power constant current charge to 10.0V; Discharge ends to 2.0V with 1C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity, and discharge and likening to of charge capacity are efficiency for charge-discharge.Fig. 2 has shown the 1C charging and discharging curve.
Embodiment 2:
Positive and negative very 2 pairs, the charging cut-ff voltage is 6.5V, and discharge is by 1.5V, and all the other are identical with embodiment 1, repeats above test, and outcome record is in table 1.
Comparative Examples 1:
Both positive and negative polarity adopts two-sided traditional structure of filming, and the charging cut-ff voltage is 3.2V, and discharge is by 1V, and all the other are identical with embodiment 1, repeats above test, and outcome record is in table 1.
Table 1
| Project | Anodal | Negative pole (mass ratio, Li 4Ti 5O 12/AC) | Electrode structure | Discharge voltage (V) | Capacity (mAh) |
| Embodiment 1 | Ternary | 4/1 | Bipolarity, 3 pairs | 8.5 | 6.3 |
| Embodiment 2 | Ternary | 4/1 | Bipolarity, 2 pairs | 5.7 | 6.4 |
| Comparative Examples 1 | Ternary | 4/1 | The tradition lamination, 3 pairs | 2.8 | 20 |
From above result as can be known:, adopt tertiary cathode material, lithium titanate to have high voltage and the adjustable characteristics of voltage with the bipolarity electrochemical energy storage and the energy conversion device of active carbon mixing negative material owing to be equivalent to the cell cascaded structure between bipolar electrode of the present invention; And the electrochemical energy storage device of the Comparative Examples 1 of traditional structure is a parallel-connection structure, and voltage and electrode number are irrelevant.Simultaneously, adopt bipolar structure, the number of collector is equivalent to reduce by half, and has reduced the weight of electric core, can improve the gravimetric specific energy of energy storage device.Therefore electrode structure of the present invention, discharge and recharge mechanism and energy storage device and constitute and have novelty, and monomer voltage adjusting, reliability, specific energy and fail safe are had tangible effect.
Claims (5)
1. an electrochemical energy storage and energy conversion device with bipolar structure, comprise bipolar electrode, barrier film and nonaqueous electrolyte, it is characterized in that: a side of described bipolar electrode collector is an anode active material of lithium ion battery, contains the lithium ion transistion metal compound that can absorb/emit lithium ion; Opposite side is a capacitor anode material, contains oxidation-reduction potential and is higher than 1.0Vvs.Li/Li
+Lithium ion battery active material and the mixture or the compound of activated carbon.
2. electrochemical energy storage and the energy conversion device with bipolar structure according to claim 1 is characterized in that: described anode active material of lithium ion battery is Li (NiCoMn) O
2
3. electrochemical energy storage and the energy conversion device with bipolar structure according to claim 1 is characterized in that: described capacitor anode material is the mixture/compound of lithium titanate and activated carbon.
4. electrochemical energy storage and the energy conversion device with bipolar structure according to claim 1 is characterized in that: described collector is an aluminum foil current collector.
5. according to the electrochemical energy storage with bipolar structure and the energy conversion device of claim 1, it is characterized in that: described barrier film is the colloidal electrolyte film.
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|---|---|---|---|
| CN2010101293622A CN102201605A (en) | 2010-03-22 | 2010-03-22 | Electrochemical energy storage and conversion device having bipolar structure |
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|---|---|---|---|
| CN2010101293622A CN102201605A (en) | 2010-03-22 | 2010-03-22 | Electrochemical energy storage and conversion device having bipolar structure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN110137577A (en) * | 2019-06-04 | 2019-08-16 | 广东省飞驰新能源科技有限公司 | It is a kind of can high current charge-discharge iron phosphate polymer lithium lithium battery |
| CN111640582A (en) * | 2020-06-16 | 2020-09-08 | 中国科学院电工研究所 | High-voltage electrochemical capacitor, preparation method and energy storage module thereof |
| CN112310469A (en) * | 2019-07-26 | 2021-02-02 | 通用汽车环球科技运作有限责任公司 | Capacitor assisted bipolar battery |
| CN112567552A (en) * | 2018-07-11 | 2021-03-26 | 原子能和替代能源委员会 | Electrochemical storage cell with bipolar structure comprising specific structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1499664A (en) * | 2002-11-07 | 2004-05-26 | �ղ��Զ�����ʽ���� | Bipolar cell |
| CN101110477A (en) * | 2006-07-18 | 2008-01-23 | 中国电子科技集团公司第十八研究所 | Electro-chemistry energy storing and converting device |
-
2010
- 2010-03-22 CN CN2010101293622A patent/CN102201605A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1499664A (en) * | 2002-11-07 | 2004-05-26 | �ղ��Զ�����ʽ���� | Bipolar cell |
| CN101110477A (en) * | 2006-07-18 | 2008-01-23 | 中国电子科技集团公司第十八研究所 | Electro-chemistry energy storing and converting device |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112567552A (en) * | 2018-07-11 | 2021-03-26 | 原子能和替代能源委员会 | Electrochemical storage cell with bipolar structure comprising specific structure |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN110137577A (en) * | 2019-06-04 | 2019-08-16 | 广东省飞驰新能源科技有限公司 | It is a kind of can high current charge-discharge iron phosphate polymer lithium lithium battery |
| CN110137577B (en) * | 2019-06-04 | 2020-12-08 | 广东省飞驰新能源科技有限公司 | Lithium iron phosphate polymer lithium battery capable of realizing large-current charging and discharging |
| CN112310469A (en) * | 2019-07-26 | 2021-02-02 | 通用汽车环球科技运作有限责任公司 | Capacitor assisted bipolar battery |
| CN111640582A (en) * | 2020-06-16 | 2020-09-08 | 中国科学院电工研究所 | High-voltage electrochemical capacitor, preparation method and energy storage module thereof |
| CN111640582B (en) * | 2020-06-16 | 2022-11-15 | 中国科学院电工研究所 | High-voltage electrochemical capacitor, preparation method and energy storage module thereof |
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Application publication date: 20110928 |