A kind of power MH-Ni battery production method and equipment of Nanocrystaline spherical nickel hydroxide
Technical field
The present invention relates to the manufacture method and the equipment thereof of a kind of sphere or class ball-shape nickel hydroxide, especially a kind ofly add nickel salt solution and alkaline solution and concentrated ammonia solution in the reactor continuously, and overflow from overflow port continuously, reach the control nickel hydroxide and grow up to sphere or class sphere, its product structure is that nanocrystalline, loose density is that 1.80g/ml is above, tap density is the production method and the producing apparatus of the Nanocrystaline spherical nickel hydroxide used of the above power MH-Ni of 2.35g/ml battery.
Background technology
Nickel hydroxide powder mainly is used as the positive electrode active materials of Cd-Ni and MH-Ni battery and alkaline cell etc., general method for making is at present: the nickel salt aqueous solution that the caustic solution of caustic soda and Ke Xingjia etc. is acted on nickelous nitrate and single nickel salt etc. under the prerequisite that has ammoniacal liquor to exist, and directly add above reaction raw materials in the reactor, in reaction process, by adding concentration and add-on, the system pH value etc. of various materials in the fixed system, produce sphere or class ball-shape nickel hydroxide precipitation, obtain nickel hydroxide through operations such as solid-liquid separation, washing, dryings then.The nickel hydroxide that obtains like this is difficult to satisfy the requirement of high tamped density of modern MH-Ni battery and high-capacitance, especially is difficult to satisfy the requirement of the high life of power MH-Ni battery, high low temperature charge-discharge performance, high rate during charging-discharging.Its basic reason is that reaction product is an ordinary hydrogen nickel oxide (see figure 1), and therefore, traditional ordinary hydrogen nickel oxide and production method are difficult to satisfy the requirement of present power cell.
Day disclosure special permission spy opens the manufacture method that flat 8-119636 has announced nickel hydroxide: nickel salt solution, caustic solution, the directly continuous injecting reactor of ammonia soln are also stirred simultaneously.The pH value of control reaction system in the reaction process.When question response liquid reaches the reaction vessel capacity, remove medium liquid in the reaction system, make reaction solution minimizing in the reaction system, continue to inject nickel salt solution, caustic solution, ammonia soln then.After repeatable operation, generate nickel hydroxide.Obtain the product tap density and reach 1.9-2.2g/ml.Though the production control method of this nickel hydroxide can access the product that has than high tap density, but the nickel hydroxide that obtains is the ordinary hydrogen nickel oxide, it can not satisfy the requirement of modern power MH-Ni battery with heavy body and high life nickel hydroxide, and troublesome poeration, and production efficiency is low.
Day disclosure special permission spy opens the up-to-date method for making that flat 9-283135 has announced nickel hydroxide: at the synthetic groove that is having synthetic nickel ammine, the reactor that the nickel hydroxide reaction solution overflows continuously, its reaction obtains the nickel hydroxide tap density and reaches 2.0g/ml, and its interior tissue is periodical change.The product that this production control method obtains still can not satisfy the needs of power MH-Ni nickel hydroxide for cells, and the nickel hydroxide that obtains is the ordinary hydrogen nickel oxide, and its quality product is unsettled in one-period.
Summary of the invention
The object of the present invention is to provide a kind of production method and producing apparatus of being convenient to the power MH-Ni battery of suitability for industrialized production with the ball-shape nickel hydroxide powder.By the CONTROL PROCESS condition, can produce the product of nanocrystal bundle size below 100nm of nickel hydroxide, its loose density more than 1.80g/ml, the Nanocrystaline spherical nickel hydroxide used at the above power MH-Ni of 2.35g/ml battery of tap density.
The invention provides a kind of power MH-Ni battery with Nanocrystaline spherical nickel hydroxide production method, nickel salt solution and alkaline solution and concentrated ammonia solution are joined in the reactor cycles pipe continuously, and overflow from overflow port continuously; Reactant feed concentration be following scope fixed value: a 1.7~2.1mol/l the single nickel salt salts solution and contain rose vitriol that concentration is nickel volumetric molar concentration 2-5% and zinc sulfate mixed salt solution and strong aqua and the caustic solution of 5-9%; Reactor temperature is a certain fixed value between 40-60 ℃ and be controlled at ± 1 ℃; PH value is a certain fixed value between the 11.0-11.5 and be controlled at ± 1; The reinforced mol ratio of ammonia nickel is M in reaction process
NH3H2O: M
Ni2+=0.5-0.9: 1; The reaction system stirring velocity is 100-300 rev/min.
The concentration of above-mentioned caustic alkali is 6-9mol/L.
The density of above-mentioned strong aqua is 0.88-0.92g/ml.
The add-on of mixed sulfate is 100-200L/h in the above-mentioned reaction process, and optimal addn is 140-160L/h.
The flow of above-mentioned reaction product in circulation tube is that flow hourly is 3-8 a times of reactor volume, and linear rate of flow is 100-800m/min.
The reinforced mol ratio the best of ammonia nickel is M in the above-mentioned reaction process
NH3H2O: M
Ni2+=0.7-0.9: 1.
A kind of power MH-Ni battery is made up of main reactor, circulation tube, recycle pump and overflow port with the production unit of Nanocrystaline spherical nickel hydroxide, is provided with whipping appts in the main reactor, and the appropriate location of one side is provided with overflow port; Circulation tube one end is from being inserted in the main reactor, and the other end is welded on the bottom of main reactor; The circulation tube upper end is a feeding section, and is provided with three filling tubes, and the bottom is provided with a recycle pump.
The diameter of above-mentioned circulation tube feeding section is greater than the diameter of two ends circulation tube.
Also be provided with PH meter and thermometer on the above-mentioned circulation tube feeding section.
Major advantage of the present invention is:
1. reaction conditions of the present invention is easy to control, and manual operations can be produced the power type MH-Ni battery Nanocrystaline spherical nickel hydroxide powder product of stable performance; The nickel hydroxide powder of producing is nanocrystalline, and as shown in Figure 2, this nickel hydroxide powder density is big, and loose density and tap density height can reach 1.80g/ml respectively and more than the 2.35g/ml; Quality product is continual and steady, as electrode active material and the mashed prod good fluidity of making after conductive agent mixes, tamped density height, its Nanocrystaline spherical nickel hydroxide product good electrical property, long service life.The 1C loading capacity can reach more than the 260mah/g after this product was made power type MH-Ni battery, and mean lifetime reached more than 500 weeks.
2. the maximum difference of reactor provided by the present invention and traditional reactor is: increased circulation tube (2) and mixed sulfate filling tube (3), caustic alkali filling tube (4) and ammoniacal liquor filling tube (5) are installed on the circulation tube than traditional reactor, thereby guarantee that reaction raw materials can react fully in circulation tube, and guarantee to form the Nanocrystaline spherical nickel hydroxide.
Description of drawings
Fig. 1 is a general spherical shape nickel hydroxide photo;
Fig. 2 is the Nanocrystaline spherical nickel hydroxide photo that the present invention produces;
Fig. 3 is the nickel hydroxide photo that the embodiment of the invention 1 reaction generates;
Fig. 4 is the nickel hydroxide photo that the embodiment of the invention 2 reactions generate;
Fig. 5 is the structural representation of the production unit of Nanocrystaline spherical nickel hydroxide of the present invention.
Embodiment
Reactor of the present invention is seen Fig. 5.This reactor comprises: main reactor whipping appts (1), circulation tube (2) (arrow is represented the Flow of Goods and Materials direction in the reaction tubes), mixed sulfate filling tube (3), caustic alkali filling tube (4), ammoniacal liquor filling tube (5), PH meter (6), thermometer (7), reaction product recycle pump (8), main reactor (9), overflow port (10), circulation tube feeding section (11).Be provided with whipping appts (1) in the main reactor (9), the appropriate location of one side is provided with overflow port (10); Circulation tube (2) one ends are from being inserted in the main reactor (9), and the other end is welded on the bottom of main reactor (9); The circulation tube upper end is feeding section (11), and is provided with three filling tubes (3), (4), (5), is used for the adding respectively of raw material, and the bottom is provided with a recycle pump (8).Wherein, the diameter of circulation tube feeding section (11) is greater than the diameter of two ends circulation tube (2); PH meter (6) and thermometer (7) are located on the circulation tube feeding section (11).
PH meter (6) and thermometer (7) also can be placed directly in the main reactor.
Embodiment 1:
Reactor volume 2m
3, reaction soln is that concentration is the mixed sulfate solution of 2.0mol/L single nickel salt, 0.06mol/L rose vitriol, 0.12mol/L zinc sulfate, and the sodium hydroxide solution volumetric molar concentration is 8.0mom/l, and ammoniacal liquor density is 0.88-0.92g/ml.During reaction, mixed sulfate and alkaline solution and concentrated ammonia solution are directly added three filling tubes (3), (4), (5) from the circulation tube feeding section (11) of reactor continuously, the add-on of mixed sulfate is 150L/h in the reaction process, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=0.7: 1, the pH value of reaction system is controlled at 11.0 ± 0.1, and temperature of reaction is 45 ± 1 ℃.Adjusting the stirring velocity scope in the reaction is 230rpm, and the flow of reaction product is 10m in the circulation tube (2)
3/ h, linear rate of flow are 300m/min, and the crystal grain bundle of reaction back nickel hydroxide is of a size of the 80nm (see figure 3).The loose density of reaction back Nanocrystaline spherical nickel hydroxide is that 1.83g/Ml, tap density are 2.42g/ml.The Nanocrystaline spherical nickel hydroxide make battery after test, its 1C loading capacity is 265mAh/g, cycle life was 580 weeks.
Embodiment 2:
Reactor volume 2m
3, reaction soln is that concentration is the mixing solutions of 1.8mol/L single nickel salt, 0.045mol/L rose vitriol, 0.126mol/L zinc sulfate, and the sodium hydroxide solution volumetric molar concentration is 6.0mom/l, and ammoniacal liquor density is 0.88-0.92g/ml.During reaction, mixed sulfate and alkaline solution and concentrated ammonia solution are directly added three filling tubes (3), (4), (5) from the circulation tube feeding section (11) of reactor continuously, the add-on of mixed sulfate is 150L/h in the reaction process, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=0.9: 1, the pH value of reaction system is controlled at 11.3 ± 0.1, and temperature of reaction is 50 ± 1 ℃.Adjusting the stirring velocity scope in the reaction is 280rpm, and the flow of reaction product is 12.5m in the circulation tube (2)
3/ h, linear rate of flow are 400m/min, and the crystal grain bundle mean sizes of reaction back nickel hydroxide is the 60nm (see figure 4).The loose density of reaction back Nanocrystaline spherical nickel hydroxide is that 1.85g/ml, tap density are 2.46g/ml.The Nanocrystaline spherical nickel hydroxide make battery after test, its 1C loading capacity is 268mAh/g, cycle life was 630 weeks.
Embodiment 3:
Reactor volume 2m
3, reaction soln is that concentration is the mixed sulfate solution of 1.7mol/L single nickel salt, 0.085mol/L rose vitriol, 0.153mol/L zinc sulfate, and the sodium hydroxide solution volumetric molar concentration is 7.0mom/l, and ammoniacal liquor density is 0.88-0.92g/ml.During reaction, mixed sulfate and alkaline solution and concentrated ammonia solution are directly added three filling tubes (3), (4), (5) from the circulation tube feeding section (11) of reactor continuously, the add-on of mixed sulfate is 100L/h in the reaction process, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=0.5: 1, the pH value of reaction system is controlled at 11.4 ± 0.1, and temperature of reaction is 40 ± 1 ℃.Adjusting the stirring velocity scope in the reaction is 100rpm, and the flow of reaction product is 6m in the circulation tube (2)
3/ h, linear rate of flow are 100m/min, and the crystal grain bundle of reaction back nickel hydroxide is of a size of 90nm.The loose density of reaction back Nanocrystaline spherical nickel hydroxide is that 1.82g/Ml, tap density are 2.40g/ml.
Embodiment 4:
Reactor volume 2m
3, reaction soln is that concentration is the mixed sulfate solution of 2.1mol/L single nickel salt, 0.042mol/L rose vitriol, 0.105mol/L zinc sulfate, and the sodium hydroxide solution volumetric molar concentration is 9.0mom/l, and ammoniacal liquor density is 0.88-0.92g/ml.During reaction, mixed sulfate and alkaline solution and concentrated ammonia solution are directly added three filling tubes (3), (4), (5) from the circulation tube feeding section (11) of reactor continuously, the add-on of mixed sulfate is 200L/h in the reaction process, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=0.8: 1, the pH value of reaction system is controlled at 11.5 ± 0.1, and temperature of reaction is 60 ± 1 ℃.Adjusting the stirring velocity scope in the reaction is 300rpm, and the flow of reaction product is 16m in the circulation tube (2)
3/ h, linear rate of flow are 800m/min, and the crystal grain bundle of reaction back nickel hydroxide is of a size of 70nm.The loose density of reaction back Nanocrystaline spherical nickel hydroxide is that 1.87g/Ml, tap density are 2.49g/ml.