CN102780049A - High-capacity sodium-nickel-chloride unit flat plate battery and battery pack thereof - Google Patents
High-capacity sodium-nickel-chloride unit flat plate battery and battery pack thereof Download PDFInfo
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- CN102780049A CN102780049A CN201210285477XA CN201210285477A CN102780049A CN 102780049 A CN102780049 A CN 102780049A CN 201210285477X A CN201210285477X A CN 201210285477XA CN 201210285477 A CN201210285477 A CN 201210285477A CN 102780049 A CN102780049 A CN 102780049A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a high-capacity sodium-nickel-chloride unit flat plate battery and a battery pack thereof. The battery is composed of two cathode chambers, an anode chamber and anode and cathode terminals, wherein the anode chamber is arranged between the two cathode chambers; a cathode cover, a metal spring piece, a metal felt or a graphite felt are sequentially arranged inside each cathode chamber from outside to inside; the anode chamber is filled with an anode layer, a current collector is arranged at the center of the anode layer and penetrates through the whole anode layer, and all round of the anode chamber is fixedly sealed by an anode sealing ring; the anode chamber and the cathode chambers are separated through solid electrolytes; and an anode electrode bar connected onto the current collector stretches out of the anode sealing ring to form an anode terminal, and a cathode electrode bar stretches out of the cathode cover to form a cathode terminal. The battery pack comprises unit batteries, a temperature regulating system, a battery pack insulating layer, a battery pack casing and a whole battery control system sequentially from inside to outside, wherein the amount of the unit batteries is 2-100. According to the battery and the battery pack thereof, the unit battery has a large capacity, the operating temperature is low, the structure is simple, the production is convenient, and the cost is low.
Description
Technical field
The present invention relates to a kind of battery and battery pack thereof, more specifically to a kind of big capacity sodium nickel chloride single flat plate cell and battery pack thereof.
Background technology
Sodium nickel chloride battery comes from sodium-sulphur battery, with sodium-sulphur battery many similarities is arranged: be β like solid electrolyte "-Al
2O
3, negative pole is liquid metal sodium.Difference is positive pole, and sodium nickel chloride battery is to soak at fusion NaAlCl
4In solid nickel/nickel chloride replaced the liquid sulfur/sodium polysulfide in the sodium-sulphur battery.Sodium nickel chloride battery has kept advantages such as the big capacity of sodium-sulphur battery, high conversion efficiency, no self discharge, also possesses inherence based on himself chemical composition and overcharges/cross and put defencive function.The whole system capacity density of sodium nickel chloride battery reaches 120Wh/kg, and power density reaches 180W/kg and lithium ion battery is suitable.Its long service life, monomer cycle life are greater than 3000 times, and battery pack can reach 1800 times.The non-maintaining stable operation 7 years on electric automobile of existing sodium nickel chloride battery, operating range reaches 112,000 kilometers.Negative pole sodium is in the battery cyclic process, to generate, and sodium nickel chloride battery is assembled under discharge condition, and is easy to operate.This battery can be charged to 50%SOC in 30 minutes fast.Compare with sodium-sulphur battery, sodium nickel chloride battery avoided sulphur when high temperature to the corrosion of battery component, improved the cycle life and the security performance of battery.Sodium nickel chloride battery is at present unique secondary battery system through ACEA (EuropeanAutomotive Industry) and all safety tests of United States advanced battery associating association (USABC).Sodium nickel chloride cell preparation cost is lower than nickel chromium triangle, ni-mh and lithium ion battery, and whole battery is non-maintaining all-sealed structure, has the low characteristics of maintenance cost.
But the shortcoming that sodium nickel chloride battery exists internal resistance to increase with degree of discharge.The resistance of this battery is from following three parts: negative pole and battery metal parts, alumina ceramic tube, positive pole.Wherein, preceding portions of resistance is a fixed value; And anodal part internal resistance meeting increases and sharply increases with degree of discharge; Reason is: 1) internal reaction forward position, anodal chamber can be moved to the center collector from the earthenware inwall with the carrying out of discharge, thereby causes anodal part internal resistance to increase along with the increase of sodium ion migration distance; 2) anodal surface chlorination nickel layer thickness also can cause anodal part internal resistance to strengthen along with the carrying out of discharge with the carrying out and increase of discharge.Sodium nickel chloride battery adopts cylindrical ceramic tubes usually at present; Power demand density in the time of reaching actual use for the assurance battery; Usually (common 20 ~ 30mm) reduce anodal thickness, and make ceramic electrolyte into cruciate flower shape to increase earthenware and anodal contact area from pipe, reduce the unit are interface resistance to adopt little caliber; And the cruciate flower earthenware can reduce anodal thickness, shortens sodium ion migration distance.Directly will strengthen earthenware prepares difficulty to tubule, and the pipe range (usually less than 300mm) in the restriction actual fabrication process causes present sodium nickel chloride battery volume less than normal, and the monocell capacity is many at 32 ~ 64Ah.As stated, adopt cylindrical or cruciate flower shape tubule footpath earthenware not only makes forming process of ceramics and sintering complicated process of preparation, and cause the cell capacity on the low side, limited the application of sodium nickel chloride battery.Simultaneously tubular ceramic needs certain wall thickness keep its mechanical strength, and generally at 1.5 ~ 2mm, thereby the internal resistance that has strengthened alumina ceramic tube makes battery operation temperature drift (270 ~ 350 ℃).Therefore, how developing big capacity sodium nickel chloride single battery, further widen its application, is present sodium nickel chloride battery industry problem demanding prompt solution.
Summary of the invention
The invention solves the problems and shortcomings that exist in the prior art, a kind of big capacity sodium nickel chloride single flat plate cell is provided, the present invention also provides a kind of big capacity sodium nickel chloride flat plate cell group.
Technical scheme of the present invention is following: a kind of big capacity sodium nickel chloride single flat plate cell, it is characterized in that forming by two negative pole chambers, anode chamber and positive and negative terminal, and anode chamber is between two negative pole chambers; Wherein, the negative pole chamber is made up of negative pole capping 1, metal spring sheet 2, metal felt or graphite felt 3 from outside to inside successively; Fill positive electrode layer 5 in the anode chamber, collector 6 is positioned at the positive electrode layer center, and runs through whole positive electrode layer, and anode chamber is all around by anodal sealing ring 7 fixing seals; Separate through solid electrolyte 4 between the both positive and negative polarity chamber; The anode electrode rod that is connected on the collector stretches out anodal sealing ring 7 formation positive terminals, and the negative electrode rod stretches out negative pole capping 1, constitutes negative terminal.
Big capacity sodium nickel chloride single flat plate cell of the present invention, its battery capacity is 200Ah ~ 2000Ah, much larger than traditional cylindrical sodium nickel chloride battery (32 ~ 64Ah).The battery normal working temperature is lower than traditional cylindrical sodium nickel chloride battery operational temperatures (270 ~ 350 ℃) between 220 and 300 ℃.
Preferred battery be shaped as cylinder, cuboid or square.Preferred negative pole capping 1 is ceramic material or metal material, more preferably aluminium oxide, zirconia, stainless steel or nickel.
Preferred said metal spring sheet 2 is pure nickel, nickel plating stainless steel or nickel-clad copper; Metal felt or graphite felt 3 are selected pure nickel felt, nickel plating stainless steel felt, nickel-clad copper felt or graphite felt for use; Metal spring sheet 2 and metal felt or graphite felt 3 shapes all change with cell shapes, and for circular or square, wherein metal spring sheet 2 can reach metal felt or graphite felt 3 and the solid electrolyte 4 tight purposes that contact.
Preferred solid electrolyte 4 is circular, square or rectangular thin slice; Thickness is at 0.1mm ~ 2mm, and preferred 0.5 ~ 1mm, area are 12463 ~ 81714mm
2Material is a sodium aluminate.
Preferred positive electrode layer 5 is by NaAlCl
4-NaCl-nickel porous constitutes.Preferred anodal sealing ring 7 is ceramic material, more preferably α-Al
2O
3Or ZrO
2, its shape changes with cell shapes.
Preferred described positive and negative electrode rod and collector 6 are all selected nickel or nickel plating metal (wherein the metal of nickel plating metal is preferably copper, silver or stainless steel) for use.
Sealing between wherein said negative electrode rod and the negative pole capping 1 is realized by hot pressing Diffusion Welding or laser welding process; Sealing between anode electrode rod and the anodal sealing ring 7 is realized by the hot pressing diffusion technology for welding.
Sealing between described solid electrolyte 4 and the anodal sealing ring 7 realizes through glass sealing process or crunch seal technology.
Sealing between described anodal sealing ring 7 and the negative pole capping 1 is realized by hot pressing Diffusion Welding or glass/ceramic process for sealing.
The present invention also provides a kind of big capacity sodium nickel chloride flat plate cell group; Be followed successively by the described cell of claim 1 11, humidity control system 12, battery pack heat insulation layer 10, battery-pack exterior casing 8 and whole battery control system 9 from inside to outside, wherein the quantity of cell is 2～100.
Preferred described battery shapes is cylindrical or rectangle; Described battery pack heat insulation layer is aerosil heat insulation layer, ceramic blankets heat insulation layer or fibrous glass insulation layer; Described battery-pack exterior casing is mild steel, pure nickel or nickel plating stainless steel; Described battery pack internal work temperature is regulated by temperature control system between 220 ℃-300 ℃.
Beneficial effect:
Replace the tubulose electrolyte with the chip solid electrolyte, can promptly not increase under the situation of anodal part internal resistance, prepare big capacity sodium nickel chloride single battery (200 ~ 2000Ah) through increasing dull and stereotyped electrolyte area in the transmission range that does not increase between the both positive and negative polarity.Simultaneously, thinner (less than the 1mm) that the chip solid electrolyte can be done reduces operating temperature (220-300 ℃) thereby further reduce the internal resistance of electrolyte part, helps reducing the operating cost of battery.Entire cell is made under normal temperature condition, and is simple to operate, and the negative pole sodium metal circulates in original position generation in the negative pole chamber through battery.The slab construction of cell makes it in groups the time, possess the advantage of combined and instant.
Big capacity sodium nickel chloride single flat plate cell of the present invention; Put except that having general sodium nickel chloride battery overcharging resisting/mistake; Long service life, outside the advantage such as security performance is good, also possess following characteristics: the cell capacity is big; Be 200Ah ~ 2000Ah, much larger than traditional cylindrical sodium nickel chloride battery (32 ~ 64Ah); The operating temperature interval is 220 ~ 300 ℃, is lower than traditional cylindrical sodium nickel chloride battery operational temperatures (270 ~ 350 ℃); Simple in structure, easy to make, cost is lower etc.This battery can be used as the power source of oily electric hybrid vehicle, public transit system, boats and ships and submarine, also can be used as energy-storage battery, and very wide application prospect is arranged in urban distribution network, wind power generation and solar power generation.
Description of drawings
Fig. 1 is cell cross-sectional view among the present invention, wherein, and the anodal sealing ring of 1-negative pole capping 2-metal spring sheet 3-metal felt or graphite felt 4-solid electrolyte 5-positive electrode layer 6-collector 7-;
Fig. 2 is battery pack structure sketch map among the present invention, wherein, and 8-battery-pack exterior casing 9-control system 10-heat insulation layer 11-cell 12-humidity control system.
Embodiment
Further specify the present invention below in conjunction with embodiment, but the scope of the invention is not limited to following embodiment.
Big capacity sodium nickel chloride single battery of the present invention (its structure is as shown in Figure 1) mainly comprises two negative pole chambers and anode chamber and positive and negative terminal, and anode chamber is between two negative pole chambers.Wherein, the negative pole chamber is made up of negative pole capping, metal spring sheet, metal felt or graphite felt from outside to inside successively; Anode chamber is filled NaAlCl
4-NaCl-nickel porous positive electrode layer, collector is positioned at the positive electrode layer center, and runs through whole positive electrode layer, and anode chamber is all around by anodal sealing ring fixing seal.Separate through solid electrolyte (diameter 126mm, thickness 0.1mm) between the both positive and negative polarity chamber.Fit tightly between metal spring sheet, graphite felt and the solid electrolyte; Form capillary interstice; The motlten metal sodium that produces in the cyclic process soaks into whole solid electrolyte under capillarity, the positive electrode rod connects collector, stretches out anodal sealing ring; Negative electrode is communicated with the negative pole chamber, stretches out the negative pole capping.Battery be shaped as circle, described negative pole capping is a stainless steel, the metal spring sheet is a nickel; Collector is a nickel-clad copper, and the both positive and negative polarity electrode bar is a nickel, and the solid electrolyte cross section is circular; Material is a sodium aluminate; The chip solid electrolyte can reduce difficulty of processing, reduces resistance and anodal transmission range, improves the specific energy and the specific power of battery.Anodal sealing ring is α-Al
2O
3Seal through Diffusion Welding between sealing between anode electrode rod and the anodal sealing ring and negative pole capping and the anodal sealing ring; Be connected through laser welding between negative electrode rod and the negative pole capping, accomplish through glass sealing between solid electrolyte and the anodal sealing ring.Under 250 ℃, battery 20A discharge can continue 10h, and capacity is 200Ah.Capacity is 180Ah after this cell circulation 1000 times, capability retention 90%.The cell energy storage capacity is 0.516kWh.
Embodiment 2
Big capacity sodium nickel chloride single battery of the present invention mainly comprises two negative pole chambers and anode chamber and positive and negative terminal, and anode chamber is between two negative pole chambers.Wherein, the negative pole chamber is made up of negative pole capping, metal spring sheet, metallic nickel felt from outside to inside successively; Anode chamber is filled NaAlCl
4-NaCl-nickel porous positive electrode layer, collector is positioned at the positive electrode layer center, and runs through whole positive electrode layer, and anode chamber is all around by anodal sealing ring fixing seal.Separate through solid electrolyte (length of side 286mm, thickness 2mm) between the both positive and negative polarity chamber.Fit tightly between metal spring sheet, metallic nickel felt and the solid electrolyte; Form capillary interstice; The motlten metal sodium that produces in the cyclic process soaks into whole solid electrolyte under capillarity, the positive electrode rod connects collector, stretches out anodal sealing ring; Negative electrode is communicated with the negative pole chamber, stretches out the negative pole capping.Battery be shaped as circle, described negative pole capping is an aluminium oxide, the metal spring sheet is a nickel-clad copper, collector is a nickel, the both positive and negative polarity electrode bar is the nickel plating stainless steel, the solid electrolyte cross section is circular, material is a sodium aluminate.Anodal sealing ring is ZrO
2Under 220 ℃, battery 200A discharge sustain 10h, capacity is 2000Ah.Capacity is 1800Ah after this cell circulation 1000 times, capability retention 90%.The cell energy storage capacity is 5.42kWh.
Embodiment 3
As shown in Figure 2; A kind of big capacity sodium nickel chloride battery pack; Inner cell by 16 embodiment 1 is formed with the connection mode of 4 and 4 strings, and promptly whole battery group is composed in parallel by 4 string baby battery groups, and wherein every string baby battery group is in series by 4 cells; Outside batteries is furnished with humidity control system, battery pack heat insulation layer, battery-pack exterior casing successively, and outermost is whole battery control system.This battery is when 260 ° of C operations, and open circuit voltage is 10.3V, and capacity is 800Ah, and energy storage capacity is 8kWh.
Embodiment 4
As shown in Figure 2; Big capacity sodium nickel chloride battery pack among the present invention is followed successively by embodiment 1 described cell, humidity control system, battery pack heat insulation layer, battery-pack exterior casing and whole battery control system from inside to outside; Wherein cell quantity is 100, and connected mode is series connection.Described battery shapes is cylindrical; Described battery pack heat insulation layer is the aerosil heat insulation layer; Described battery-pack exterior casing is a mild steel; Described battery pack internal work temperature is regulated by temperature control system between 220 ℃-300 ℃.This battery pack is when 300 ℃ of operations, and open circuit voltage is 258V, and capacity is 200Ah, and energy storage capacity is 51.6kWh.
Embodiment 5
As shown in Figure 2; Big capacity sodium nickel chloride battery pack among the present invention is followed successively by embodiment 2 described cells, humidity control system, battery pack heat insulation layer, battery-pack exterior casing and whole battery control system from inside to outside; Wherein cell quantity is 10, and connected mode is series connection.Described battery shapes is cylindrical; Described battery pack heat insulation layer is the ceramic blankets heat insulation layer; Described battery-pack exterior casing is a nickel; Described battery pack internal work temperature is regulated by temperature control system between 220 ℃-300 ℃.This battery pack is when 220 ℃ of operations, and open circuit voltage is 26V, and capacity is 2000Ah, and energy storage capacity is 54.18kWh.
Claims (9)
1. one kind big capacity sodium nickel chloride single flat plate cell is characterized in that being made up of two negative pole chambers, anode chamber and positive and negative terminal, and anode chamber is between two negative pole chambers; Wherein, the negative pole chamber is made up of negative pole capping (1), metal spring sheet (2), metal felt or graphite felt (3) from outside to inside successively; Fill positive electrode layer (5) in the anode chamber, collector (6) is positioned at the positive electrode layer center, and runs through whole positive electrode layer, and anode chamber is all around by anodal sealing ring (7) fixing seal; Separate through solid electrolyte (4) between the both positive and negative polarity chamber; The anode electrode rod that is connected on the collector stretches out anodal sealing ring (7) formation positive terminal, and the negative electrode rod stretches out negative pole capping (1), constitutes negative terminal.
2. big capacity sodium nickel chloride single battery according to claim 1 is characterized in that battery capacity is 200Ah ~ 2000Ah; The battery normal working temperature is between 220 ~ 300 ℃.
3. big capacity sodium nickel chloride single battery according to claim 1, what it is characterized in that battery is shaped as cylinder, cuboid or square.
4. big capacity sodium nickel chloride single battery according to claim 1 is characterized in that described negative pole capping (1) is ceramic material or metal material; Described metal spring sheet (2) is selected pure nickel, nickel plating stainless steel or nickel-clad copper for use; Metal felt or graphite felt (3) are selected pure nickel felt, nickel plating stainless steel felt, nickel-clad copper felt or graphite felt for use, and metal spring sheet (2) and metal felt or graphite felt (3) shape all change with cell shapes.
5. big capacity sodium nickel chloride single battery according to claim 1 is characterized in that described solid electrolyte (4) is circular, square or rectangular thin slice, and thickness is at 0.1mm ~ 2mm, and preferred 0.5 ~ 1mm, area are 12463 ~ 81714mm
2Material is a sodium aluminate.
6. big capacity sodium nickel chloride single battery according to claim 1 is characterized in that described positive electrode layer (5) is by NaAlCl
4-NaCl-nickel porous constitutes; Described anodal sealing ring (7) is a ceramic material, and its shape changes with cell shapes.
7. high-energy-density sodium nickel chloride single battery according to claim 1 is characterized in that described positive and negative electrode rod and collector (6) all select nickel or nickel plating metal for use.
8. one kind big capacity sodium nickel chloride flat plate cell group; It is characterized in that: be followed successively by the described cell of claim 1 (11), humidity control system (12), battery pack heat insulation layer (10), battery-pack exterior casing (8) and whole battery control system (9) from inside to outside, wherein the quantity of cell is 2～100.
9. big capacity sodium nickel chloride battery pack according to claim 8 is characterized in that described battery shapes is cylindrical or rectangle; Described battery pack heat insulation layer is aerosil heat insulation layer, ceramic blankets heat insulation layer or fibrous glass insulation layer; Described battery-pack exterior casing is mild steel, pure nickel or nickel plating stainless steel; Described battery pack internal work temperature is between 220 ℃-300 ℃.
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| CN201210285477.XA CN102780049B (en) | 2012-08-10 | 2012-08-10 | High-capacity sodium-nickel-chloride unit flat plate battery and battery pack thereof |
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| CN201210285477.XA CN102780049B (en) | 2012-08-10 | 2012-08-10 | High-capacity sodium-nickel-chloride unit flat plate battery and battery pack thereof |
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| CN102780049B CN102780049B (en) | 2015-06-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066284A (en) * | 2013-01-17 | 2013-04-24 | 宁夏天宇光电太阳能科技有限公司 | Preparation method of negative electrode material sodium chloride of sodium nickel battery |
| CN105405993A (en) * | 2015-11-05 | 2016-03-16 | 中国科学院宁波材料技术与工程研究所 | Flat plate structured Na-Ni battery energy storage module and Na-Ni battery pack |
| CN105990614A (en) * | 2015-02-13 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Sodium-metal chloride battery with plate structure |
| CN111276762A (en) * | 2019-12-24 | 2020-06-12 | 郑州大学 | Novel lithium-ferrous chloride battery based on garnet solid electrolyte and preparation method thereof |
| CN112803104A (en) * | 2021-01-13 | 2021-05-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Pressure-resistant high-volume-ratio energy battery pack and welding method thereof |
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| CN202930503U (en) * | 2012-08-10 | 2013-05-08 | 南京工业大学 | High-capacity NaNiCl single flat battery and battery pack thereof |
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2012
- 2012-08-10 CN CN201210285477.XA patent/CN102780049B/en not_active Expired - Fee Related
Patent Citations (4)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066284A (en) * | 2013-01-17 | 2013-04-24 | 宁夏天宇光电太阳能科技有限公司 | Preparation method of negative electrode material sodium chloride of sodium nickel battery |
| CN105990614A (en) * | 2015-02-13 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Sodium-metal chloride battery with plate structure |
| CN105405993A (en) * | 2015-11-05 | 2016-03-16 | 中国科学院宁波材料技术与工程研究所 | Flat plate structured Na-Ni battery energy storage module and Na-Ni battery pack |
| CN105405993B (en) * | 2015-11-05 | 2018-09-07 | 中国科学院宁波材料技术与工程研究所 | A kind of the sodium nickel-based battery energy-storage module and sodium nickel-based battery group of flat structure |
| CN111276762A (en) * | 2019-12-24 | 2020-06-12 | 郑州大学 | Novel lithium-ferrous chloride battery based on garnet solid electrolyte and preparation method thereof |
| CN112803104A (en) * | 2021-01-13 | 2021-05-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Pressure-resistant high-volume-ratio energy battery pack and welding method thereof |
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|---|---|
| CN102780049B (en) | 2015-06-03 |
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