CN102780049B - 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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- CN102780049B CN102780049B CN201210285477.XA CN201210285477A CN102780049B CN 102780049 B CN102780049 B CN 102780049B CN 201210285477 A CN201210285477 A CN 201210285477A CN 102780049 B CN102780049 B CN 102780049B
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- battery
- nickel
- anode
- sodium
- felt
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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 high-capacity sodium-nickel-chloriunit unit flat plate battery and battery pack thereof.
Background technology
Sodium nickel chloride battery comes from sodium-sulphur battery, has many similarities with sodium-sulphur battery: as solid electrolyte is β "-Al
2o
3, negative pole is liquid metal sodium.Difference is positive pole, and sodium nickel chloride battery is to infiltrate at melting NaAlCl
4in solid nickel/nickel chloride instead of liquid sulfur/sodium polysulfide in sodium-sulphur battery.Sodium nickel chloride battery remains sodium-sulphur battery Large Copacity, high conversion efficiency, without advantages such as self discharges, the inherence also possessed based on himself chemical composition overcharges/Cross prevention function.The whole system energy densities 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 is 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 kilometer.Negative pole sodium generates in circulating battery process, and sodium nickel chloride battery is assembled in the discharged condition, easy to operate.This battery can be charged to 50%SOC in 30 minutes fast.Compare with sodium-sulphur battery, sodium nickel chloride battery avoids sulphur corrosion to battery component when high temperature, improves cycle life and the security performance of battery.Sodium nickel chloride battery is unique secondary battery system by ACEA (EuropeanAutomotive Industry) and United States advanced battery associating association (USABC) all safety tests at present.Sodium nickel chloride battery 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 advantages that maintenance cost is low.
Can sodium nickel chloride battery exist internal resistance with degree of discharge increase and increase shortcoming.The resistance of this battery is from following three parts: negative pole and battery metal parts, alumina ceramic tube, positive pole.Wherein, front portions of resistance is fixed value; And anode portion internal resistance can increase with degree of discharge and sharply increase, reason is: 1) in positive pole chamber, reaction front can move to center set fluid from earthenware inwall with the carrying out of electric discharge, thus causes anode portion internal resistance to increase along with the increase of sodium ions distance; 2) positive electrode surface nickel chloride layer thickness also can carrying out and increase with electric discharge, causes anode portion internal resistance to strengthen along with the carrying out of electric discharge.Current sodium nickel chloride battery adopts cylindrical ceramic tubes usually, power demand density during for ensureing that battery can reach actual use, usual employing pipe with small pipe diameter (usual 20 ~ 30mm) reduces positive pole thickness, and make ceramic electrolyte into cruciate flower shape to increase the contact area of earthenware and positive pole from pipe, reduce unit are interface resistance, and cruciate flower earthenware can reduce positive pole thickness, shorten sodium ions distance.Increasing earthenware is prepared difficulty by pipe with small pipe diameter, and the pipe range (being usually less than 300mm) in restriction actual fabrication process, cause current sodium nickel chloride battery volume less than normal, monocell capacity is many at 32 ~ 64Ah.As mentioned above, adopt cylindrical or cruciate flower shape pipe with small pipe diameter earthenware not only to make forming process of ceramics and sintering complicated process of preparation, and cause cell capacity on the low side, limit the application of sodium nickel chloride battery.Tubular ceramic needs certain wall thickness to maintain its mechanical strength simultaneously, generally at 1.5 ~ 2mm, thus increases the internal resistance of alumina ceramic tube, makes cell operating temperature higher (270 ~ 350 DEG C).Therefore, how developing Large Copacity sodium nickel chloride single battery, widen its application further, is current sodium nickel chloride battery industry problem demanding prompt solution.
Summary of the invention
The invention solves problems of the prior art with not enough, a kind of high-capacity sodium-nickel-chloriunit unit flat plate battery is provided, present invention also offers a kind of Large Copacity sodium nickel chloride flat plate cell group.
Technical scheme of the present invention is as follows: a kind of high-capacity sodium-nickel-chloriunit unit flat plate battery, it is characterized in that being made up of two cathode chamber, an anode chamber and positive and negative terminal, and anode chamber is between two cathode chamber; Wherein, cathode chamber is made up of negative pole capping 1, metallic spring 2, metal felt or graphite felt 3 from outside to inside successively; Fill anode layer 5 in anode chamber, collector 6 is positioned at anode layer center, and runs through whole anode layer, and anode chamber surrounding is by positive pole sealing ring 7 fixing seal; Separated by solid electrolyte 4 between both positive and negative polarity chamber; The anode electrode rod connected on a current collector stretches out positive pole sealing ring 7 and forms positive terminal, and negative electrode rod stretches out negative pole capping 1, forms negative terminal.
High-capacity sodium-nickel-chloriunit unit flat plate battery of the present invention, its battery capacity is 200Ah ~ 2000Ah, much larger than traditional cylindrical sodium nickel chloride battery (32 ~ 64Ah).Normal battery operation temperature between 220 and 300 DEG C, lower than traditional cylindrical sodium nickel chloride battery operational temperatures (270 ~ 350 DEG C).
The shape of preferred battery is 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 described metallic spring 2 is pure nickel, nickel plating stainless steel or nickel-clad copper; Metal felt or graphite felt 3 select pure nickel felt, nickel plating stainless steel felt, nickel-clad copper felt or graphite felt; Metallic spring 2 and metal felt or graphite felt 3 shape, all with cell shapes change, are circular or square, and wherein metallic spring 2 can reach the object of metal felt or graphite felt 3 and solid electrolyte 4 close contact.
Preferred solid electrolyte 4 is circular, square or rectangular thin slice; Thickness is at 0.1mm ~ 2mm, and preferably 0.5 ~ 1mm, area is 12463 ~ 81714mm
2; Material is sodium aluminate.
Preferred anode layer 5 is by NaAlCl
4-NaCl-nickel porous is formed.Preferred positive pole sealing ring 7 is ceramic material, more preferably α-Al
2o
3or ZrO
2, its shape changes with cell shapes.
Preferably described positive and negative electrode rod and collector 6 all select nickel or nickel-plated metal (wherein the metal of nickel-plated metal is preferably copper, silver or stainless steel).
Wherein said negative electrode rod and the sealing between negative pole capping 1 are welded by Hot pressing diffusion or laser welding process realizes; Sealing between anode electrode rod and positive pole sealing ring 7 is realized by Hot pressing diffusion welding procedure.
Sealing between described solid electrolyte 4 and positive pole sealing ring 7 is realized by glass sealing process or crunch seal technique.
Described positive pole sealing ring 7 and the sealing between negative pole capping 1 are welded by Hot pressing diffusion or glass/ceramic process for sealing realizes.
Present invention also offers a kind of Large Copacity sodium nickel chloride flat plate cell group, be followed successively by cell 11 according to claim 1, 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.
Preferably 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 internal battery pack working temperature, between 220 DEG C-300 DEG C, is regulated by temperature control system.
Beneficial effect:
Replace tube-shaped electrolyte matter by chip solid electrolyte matter, can the transmission range between both positive and negative polarity not increased, when namely not increasing anode portion internal resistance, preparing Large Copacity sodium nickel chloride single battery (200 ~ 2000Ah) by increasing dull and stereotyped electrolyte area.Meanwhile, thinner (being less than 1mm) that chip solid electrolyte matter can be done, reducing electrolyte part internal resistance further thus reduce operating temperature (220-300 DEG C), being conducive to the operating cost reducing battery.Whole battery is made under normal temperature condition, simple to operate, and negative metal sodium is generated at cathode chamber situ by circulating battery.The slab construction of cell makes it in groups time, possess the advantage of combined and instant.
High-capacity sodium-nickel-chloriunit unit flat plate battery of the present invention, put except having general sodium nickel chloride battery overcharging resisting/mistake, long service life, outside the advantages such as security performance is good, also possesses following characteristics: cell capacity is large, for 200Ah ~ 2000Ah, much larger than traditional cylindrical sodium nickel chloride battery (32 ~ 64Ah); Operating temperature interval is 220 ~ 300 DEG C, lower than traditional cylindrical sodium nickel chloride battery operational temperatures (270 ~ 350 DEG C); Structure is simple, and easy to make, cost is lower.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, has very wide application prospect in urban distribution network, wind power generation and solar power generation.
Accompanying drawing explanation
Fig. 1 is cell cross-sectional view in the present invention, wherein, and 1-negative pole capping 2-metallic spring 3-metal felt or graphite felt 4-solid electrolyte 5-anode layer 6-collector 7-positive pole sealing ring;
Fig. 2 is battery pack structure schematic diagram in 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 illustrate the present invention below in conjunction with embodiment, but the scope of the invention is not limited to the following examples.
Embodiment 1
Large Copacity sodium nickel chloride single battery (its structure as shown in Figure 1) of the present invention, mainly comprise two cathode chamber and an anode chamber and positive and negative terminal, anode chamber is between two cathode chamber.Wherein, cathode chamber is made up of negative pole capping, metallic spring, metal felt or graphite felt from outside to inside successively; Anode chamber fills NaAlCl
4-NaCl-nickel porous anode layer, collector is positioned at anode layer center, and runs through whole anode layer, and anode chamber surrounding is by positive pole sealing ring fixing seal.Separated by solid electrolyte (diameter 126mm, thickness 0.1mm) between both positive and negative polarity chamber.Metallic spring, to fit tightly between graphite felt and solid electrolyte, form capillary interstice, the motlten metal sodium produced in cyclic process infiltrates whole solid electrolyte under capillary action, positive electrode rod connects collector, stretch out positive pole sealing ring, negative electrode is communicated with cathode chamber, stretches out negative pole capping.The shape of battery is circular, described negative pole capping is stainless steel, metallic spring is nickel, collector is nickel-clad copper, and both positive and negative polarity electrode bar is nickel, and solid electrolyte cross section is circular, material is sodium aluminate, chip solid electrolyte matter can reduce difficulty of processing, reduces resistance and positive pole transmission range, improves specific energy and the specific power of battery.Positive pole sealing ring is α-Al
2o
3.Anode electrode rod and positive pole sealing ring between sealing and sealed by Diffusion Welding between negative pole capping and positive pole sealing ring, negative electrode rod is connected by laser welding with between negative pole capping, is completed between solid electrolyte and positive pole sealing ring by glass sealing.At 250 DEG C, battery 20A electric discharge can continue 10h, and capacity is 200Ah.This cell capacity after 1000 times that circulates is 180Ah, capability retention 90%.Cell energy storage capacity is 0.516kWh.
Embodiment 2
Large Copacity sodium nickel chloride single battery of the present invention, mainly comprise two cathode chamber and an anode chamber and positive and negative terminal, anode chamber is between two cathode chamber.Wherein, cathode chamber is made up of negative pole capping, metallic spring, metallic nickel felt from outside to inside successively; Anode chamber fills NaAlCl
4-NaCl-nickel porous anode layer, collector is positioned at anode layer center, and runs through whole anode layer, and anode chamber surrounding is by positive pole sealing ring fixing seal.Separated by solid electrolyte (length of side 286mm, thickness 2mm) between both positive and negative polarity chamber.Metallic spring, to fit tightly between metallic nickel felt and solid electrolyte, form capillary interstice, the motlten metal sodium produced in cyclic process infiltrates whole solid electrolyte under capillary action, positive electrode rod connects collector, stretch out positive pole sealing ring, negative electrode is communicated with cathode chamber, stretches out negative pole capping.The shape of battery is circular, and described negative pole capping is aluminium oxide, and metallic spring is nickel-clad copper, and collector is nickel, and both positive and negative polarity electrode bar is nickel plating stainless steel, and solid electrolyte cross section is circular, and material is sodium aluminate.Positive pole sealing ring is ZrO
2.At 220 DEG C, battery 200A discharge sustain 10h, capacity is 2000Ah.This cell capacity after 1000 times that circulates is 1800Ah, capability retention 90%.Cell energy storage capacity is 5.42kWh.
Embodiment 3
As shown in Figure 2, a kind of Large Copacity sodium nickel chloride battery pack, the inner cell by 16 embodiments 1 with 4 and the connection modes of 4 strings form, namely whole battery pack is composed in parallel by 4 string baby battery groups, baby battery group of wherein often going here and there 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 run, and open circuit voltage is 10.3V, and capacity is 800Ah, and energy storage capacity is 8kWh.
Embodiment 4
As shown in Figure 2, Large Copacity sodium nickel chloride battery pack in the present invention, is followed successively by the cell described in embodiment 1, 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 aerosil heat insulation layer; Described battery-pack exterior casing is mild steel; Described internal battery pack working temperature, between 220 DEG C-300 DEG C, is regulated by temperature control system.This battery pack is when running for 300 DEG C, and open circuit voltage is 258V, and capacity is 200Ah, and energy storage capacity is 51.6kWh.
Embodiment 5
As shown in Figure 2, Large Copacity sodium nickel chloride battery pack in the present invention, is followed successively by the cell described in embodiment 2, 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 ceramic blankets heat insulation layer; Described battery-pack exterior casing is nickel; Described internal battery pack working temperature, between 220 DEG C-300 DEG C, is regulated by temperature control system.This battery pack is when running for 220 DEG C, and open circuit voltage is 26V, and capacity is 2000Ah, and energy storage capacity is 54.18kWh.
Claims (7)
1. a high-capacity sodium-nickel-chloriunit unit flat plate battery, it is characterized in that being made up of two cathode chamber, an anode chamber and positive and negative terminal, anode chamber is between two cathode chamber; Wherein, cathode chamber is made up of negative pole capping (1), metallic spring (2), metal felt or graphite felt (3) from outside to inside successively; Fill anode layer (5) in anode chamber, collector (6) is positioned at anode layer center, and runs through whole anode layer, and anode chamber surrounding is by positive pole sealing ring (7) fixing seal; Separated by solid electrolyte (4) between both positive and negative polarity chamber; The anode electrode rod connected on a current collector stretches out positive pole sealing ring (7) and forms positive terminal, and negative electrode rod stretches out negative pole capping (1), forms negative terminal; Wherein solid electrolyte (4) is circular, square or rectangular thin slice, and thickness is at 0.5 ~ 1mm, and area is 12463 ~ 81714mm
2, material is sodium aluminate; Battery capacity is 200Ah ~ 2000Ah; Normal battery operation temperature is between 220 ~ 300 DEG C.
2. Large Copacity sodium nickel chloride single battery according to claim 1, is characterized in that the shape of battery is cylinder, cuboid or square.
3. Large Copacity 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 metallic spring (2) selects pure nickel, nickel plating stainless steel or nickel-clad copper, metal felt or graphite felt (3) select pure nickel felt, nickel plating stainless steel felt, nickel-clad copper felt or graphite felt, and metallic spring (2) and metal felt or graphite felt (3) shape all change with cell shapes.
4. Large Copacity sodium nickel chloride single battery according to claim 1, is characterized in that described anode layer (5) is made up of NaAlCl4-NaCl-nickel porous; Described positive pole sealing ring (7) is ceramic material, and its shape changes with cell shapes.
5. Large Copacity 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-plated metal.
6. a Large Copacity sodium nickel chloride flat plate cell group, it is characterized in that: be followed successively by cell according to 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.
7. Large Copacity sodium nickel chloride battery pack according to claim 6, 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 internal battery pack working temperature is between 220 DEG C-300 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN102780049A CN102780049A (en) | 2012-11-14 |
| CN102780049B true CN102780049B (en) | 2015-06-03 |
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Families Citing this family (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 |
| 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 |
| 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 |
| CN111276762B (en) * | 2019-12-24 | 2021-05-07 | 郑州大学 | Novel lithium-ferrous chloride battery based on garnet solid electrolyte and preparation method thereof |
| CN112803104B (en) * | 2021-01-13 | 2022-09-27 | 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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|---|---|---|---|---|
| CN1106575A (en) * | 1993-08-03 | 1995-08-09 | 第三程式专利集团公司 | Electrochemical cell |
| US5573873A (en) * | 1994-08-16 | 1996-11-12 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Long life NA/NiCl2 cells |
| CN101752614A (en) * | 2010-01-12 | 2010-06-23 | 南京工业大学 | Novel low-cost high-density sodium-nickel chloride single battery and battery pack thereof |
| CN202930503U (en) * | 2012-08-10 | 2013-05-08 | 南京工业大学 | High-capacity NaNiCl single flat battery and battery pack thereof |
-
2012
- 2012-08-10 CN CN201210285477.XA patent/CN102780049B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106575A (en) * | 1993-08-03 | 1995-08-09 | 第三程式专利集团公司 | Electrochemical cell |
| US5573873A (en) * | 1994-08-16 | 1996-11-12 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Long life NA/NiCl2 cells |
| CN101752614A (en) * | 2010-01-12 | 2010-06-23 | 南京工业大学 | Novel low-cost high-density sodium-nickel chloride single battery and battery pack thereof |
| 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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| CN102780049A (en) | 2012-11-14 |
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