How Can I Recycle Batteries?

Spent batteries are used and discarded batteries. The environmental impact of waste batteries and their disposal methods are still controversial. Many people think that waste batteries are serious harm to the environment and should be recycled. ^[1]

used battery

Spent batteries are used and discarded batteries. The environmental impact of waste batteries and their disposal methods are still controversial. Many people think that waste batteries are serious harm to the environment and should be recycled. ^[1]

In the past two years, the impact of waste batteries on the environment has become one of the hot topics in domestic media. Some reports claim that the battery is very polluting to the environment, and one battery can pollute 10,000 cubic meters of water. Some even say that waste batteries can cause hazards such as Japanese Minamata Disease with the disposal of domestic waste, and that a square of waste battery can make one square of land waste. Many environmentally conscious people and groups have launched or participated in activities to recycle used batteries.

Scientific investigation shows that an ordinary battery can pollute 600,000 liters of water after being thrown into the nature, which is equivalent to a person's life-long water consumption. China consumes 7 billion such batteries every year. It is understood that 96% of the batteries produced in China are zinc-manganese batteries and alkaline manganese batteries, whose main components are manganese, mercury, zinc and other heavy metals. Regardless of whether the waste battery is buried in the atmosphere or buried underground, its heavy metal components will overflow with the seepage, causing pollution of groundwater and soil, and it will also seriously endanger human health. Mercury,

From the experience of other countries, the main measure to solve the pollution in the battery industry is to adjust the product structure and eliminate backward processes and products. This is mandatory by the state. As for the collection, treatment or reuse of waste batteries, they are carried out spontaneously by industry associations, cities or enterprises. Drawing on the experience of other countries, combined with the domestic economic and technological level and the degree of market regulation, the author believes that the environmental impact of waste batteries should be scientifically understood, and its harm cannot be overstated. Relevant departments should focus on eliminating mercury-containing batteries. As for the separate collection and processing (or utilization), cities with conditions and enterprises with technical capabilities can operate it by themselves, and the state should not ask for compulsory requirements. The specific recommendations are briefly described as follows:

1. Strengthen market spot checks and enforce a ban on mercury

The target steps for phasing out mercury-containing batteries have been identified, and most companies have also done so in accordance with national requirements. However, some companies lag behind national requirements, and even a few companies use other brands to produce high-mercury batteries. These illegal acts can only be stopped by strengthening market spot checks and penalizing companies that continue to sell and produce batteries that exceed standards. It is recommended that the industry and commerce and quality supervision departments with market inspection and punishment functions take sampling tests at the sales points and find that the mercury content of the battery exceeds the standard. The inferior battery is confiscated, a fine is imposed, and the wholesaler and producer are held accountable. It is necessary to mobilize social forces to report the enterprises that produce and sell low-quality batteries through rewarding reports.

2.Carefully collect used batteries

As mentioned earlier, the mercury content in the battery is low (even high-mercury batteries), the consumer groups are scattered, and the waste batteries will not cause much pollution with the landfill of domestic waste (the protective effect of the battery case and the dilution of a large amount of garbage Effect). However, if a large amount of waste batteries are collected in one place and mishandled (such as peeling the casing, recycling valuable parts, and discarding the residue at will), it may cause mercury pollution in local areas. Therefore, some units and individuals should take proper care of the collection activities and hand them over to the units that have the conditions for storage and handling. It is not advisable to collect waste batteries on a large scale without qualified treatment or utilization facilities.

For the waste batteries that have been collected so far, the municipal environmental sanitation department shall arrange the sites for centralized storage in units of cities. After the qualified facilities are completed, they will be processed or used.

3. Resource utilization

Although it is not necessary to collect dry batteries separately from the perspective of pollution control, some units hope to recover zinc, manganese, iron and other metals from the perspective of saving resources. Like other waste comprehensive utilization projects, the scrap metal recycling industry is greatly affected by fluctuations in raw material market prices and downstream demand, and the use of waste dry batteries may not make ends meet within a certain period of time. Under the conditions of a market economy, finances are not allowed to subsidize companies that use waste batteries, and they can only adhere to the principle of voluntary companies. If the company has the technology, management capabilities, or from the perspective of public welfare, even if it is willing to do it at a loss, it can carry out this business. Mercury-containing battery recycling facilities should be built in areas with sparse populations and environmental insensitivity (such as mercury mines). The technical management level should be relatively advanced and large in scale. Avoid using them as simple workshop-type utilization plants.

It should be noted that the units engaged in the collection and utilization of waste batteries should also abide by laws and regulations on occupational disease prevention, environmental protection and land planning. Except for deductions and exemptions according to law, taxes shall be paid in accordance with the regulations. It is not possible to act in accordance with the law because of resource conservation.

4.Several suggestions for treating waste batteries

In the field of treating waste batteries, with the continuous development of the battery industry, different types and specifications of waste batteries need to be treated and processed. Therefore, we made three suggestions: solidify deep burial, store in old mines, and recycle. The recycling of waste batteries is the focus of current industry management work. Adopt the "three transformations" principle to manage used batteries, that is, to prevent and control the pollution of used batteries, and adopt the guiding ideology of reduction, resource utilization and harmlessness.

To strengthen the construction of policies and regulations on waste battery management, governments at all levels should

If, as some reports call, is it feasible to build a professional factory in China that can handle waste batteries in batches? Engineer Peng Defu from the Solid State Department of the State Environmental Protection Administration's Pollution Control Department said that to build a waste battery recycling treatment plant, An investment of more than 10 million yuan, and at least 4,000 tons of used batteries must be recycled each year before the plant can run. In fact, it is very difficult to recycle such a large amount of used batteries. Take Beijing, the capital, as an example. With strong publicity and encouragement, more than 200 tons were recovered in three years. In Hangzhou, an environmental protection model city, the recycling rate of waste batteries is only 10%. It is understood that currently two factories in Switzerland and Japan that can process and use waste batteries have been discontinued because no one is processing and using the waste batteries. This has forced us to consider carefully the question of investing in the construction of recycling plants.

Peng Defu also said that another way to deal with the centralized storage of waste batteries is to landfill or store them in accordance with the hazardous waste treatment method. However, such a treatment costs 3,000 to 4,000 yuan per ton, and it faces the problem of no cost. . It is understood that a small business in Sichuan Province is under the banner of "environmental protection". Elementary school students used a hammer to knock open the used batteries they collected on Saturday and Sunday. The valuable battery cases were recovered and sold as scrap iron. The residue is discarded at will. Waste batteries do not pose a threat to the environment. It is very important that the battery is covered with a stainless steel or carbon steel outer skin, which effectively prevents the leakage of mercury. The stainless steel or carbon steel outer skin of the waste battery was broken open, and the mercury contained in the battery was easily leaked out. As a result, the harmful substances in the battery polluted the environment and harmed the health of primary school students. This is absolutely not allowed and must be strictly prohibited.

Waste battery recycling method

Waste nickel-metal hydride battery

1.1 Recycling of failed anode alloy powder

The shell of the failed MH / Ni battery is peeled off, the negative electrode sheet is sorted from the battery cell, and the negative electrode powder is obtained by ultrasonic vibration and other physical methods. The processed negative electrode powder is obtained by chemical treatment, and the negative electrode powder is pressed into tablets. , Repeated smelting 3 to 4 times in a non-consumable vacuum arc furnace. Remove the oxide layer on the surface of the smelting ingot, crush it, and mix it uniformly. Then measure the percentage content of the mixed rare earth, nickel, cobalt, manganese, and aluminum by ICP method. According to the loss of hydrogen storage alloy elements, nickel The content of the element is used as a benchmark, and other necessary elements are added, and then smelting is performed to finally obtain a recovered alloy with excellent performance.

1.2 Recovery of MH / Ni battery negative alloy

The failed anode powder is chemically treated, and the surface of the alloy is eroded by the treatment solution to destroy the oxide on the surface of the alloy, but the corrosion of other elements that are not oxidized in the alloy and the conductive agent must be minimized. Using an acetic acid solution of 0.5 mol·L-1, the failed alloy powder was treated at room temperature for 0.5 h, then washed with distilled water and dried under vacuum. The results show that the main structure of the AB5 type hydrogen storage alloy has not changed and still belongs to the CaCu5 type hexagonal structure, but the heterogeneous phases of Al (OH) 3 and La (OH) 3 in the anode powder have completely disappeared, indicating that these oxides have been chemically After the treatment, the surface oxide was almost completely dissolved away. The charge and discharge performance of the chemically treated negative anode powder is compared with the original alloy powder for battery production and the chemically treated failed alloy powder. The discharge specific capacity of the chemically treated negative anode powder is lower than that of the chemically untreated failure. The anode powder is 23mAh · g-1 high, which indicates that after chemical treatment, most of the surface oxides are removed, which increases the effective components of the hydrogen storage alloy in the failed anode powder. The XPS test results show that the concentration of nickel atoms on the surface of the negative electrode powder increased from 6.79% before chemical treatment to 9.30%, which indicates that after chemical treatment, a nickel-rich layer with high electrocatalytic activity was formed on the surface of the alloy. The electrocatalytic activity of the hydrogen storage electrode is improved, and a diffusion path of hydrogen atoms is also provided, thereby improving the discharge performance of the electrode. However, compared with the original alloy powder used for making batteries, the chemically treated negative anode powder still has a lower discharge specific capacity of 90mAh · g-1. On the one hand, it may be due to the oxidation of the alloy is not limited to the surface, but may also penetrate into Inside the alloy, the chemical treatment only removes the surface oxides, and the deep oxidation inside the particles has not been completely removed; on the other hand, it may be due to the pulverization of the alloy to increase the specific surface area, and at the same time, the alloy reacts with O2 and is affected by The corrosion of the electrolyte is easier, and the discharge performance of the alloy is reduced due to the combination of two reasons. Therefore, only the chemical treatment method cannot restore the function of the failed anode, and smelting treatment is required.

The above-mentioned chemically treated negative electrode powder is smelted for the first time in a non-consumable arc furnace. After polishing the obtained alloy ingot, removing surface impurities, analyzing the content of each element, it can be seen that the element content in the alloy deviates from the original alloy, and the nickel content is much larger than the nickel content in the original alloy powder, which is because of the process of making the electrode Nickel powder is added as a conductive agent. In order to effectively use it, the content of other elements is adjusted to conform to the proportion of each element with the composition of MmNi3.5Co0.7Mn0.4Al0.3 for the second smelting. . After smelting, the obtained alloy ingot was broken, and after grinding, the structure was measured, and it was CaCu5 type, and no other heterogeneous phase was formed.

When the recovered alloy powder is tested for charge and discharge performance, it can be seen that the discharge capacity of the recovered alloy powder is about 100mAh · g-1 higher than that of the failed anode powder, which is basically the same as the discharge capacity of the original alloy powder. The discharge plateau pressure is about 20mV higher than the discharge plateau pressure of the original alloy powder. This may be due to the improvement of the composition and microstructure of the alloy after several melting during the alloy recovery process.

Waste lithium ion secondary battery

The process of alkali dissolution acid leaching P204 extraction purification P507 extraction and separation of cobalt and lithium back-extraction recovery of cobalt sulfate and raffinate deposition to recover lithium carbonate is used to recover cobalt and lithium from waste lithium ion secondary batteries. The experimental results show that approximately 90% of aluminum can be removed in advance by alkali dissolution, and the recovery rate of cobalt leaching from the H2SO4 + H2O2 system reaches more than 99%. After P204 extraction and purification, the impurity content is Al3.5mg / L, Fe0.5mg / L, Zn0 .6mg / L, Mn2.3mg / L, Ca <0.1mg / L; extraction and separation of cobalt and lithium with P507, at pH 5.5, the separation factor Co / Li can be as high as 1 × 105; saturated sodium carbonate above 95 ° C Lithium carbonate is deposited, and the obtained lithium carbonate can reach the requirements of zero-grade products. The primary lithium precipitation rate is 76.5%.

Lithium-ion secondary batteries are composed of a casing and an internal battery cell. The casing is a stainless steel, nickel-plated metal steel shell, or a plastic casing. The battery's internal cell is a rolled structure, which is mainly composed of a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode material of a general battery is composed of about 90% lithium cobaltate active material, 7% to 8% acetylene black conductive agent, and 3% to 4% organic binder, which are uniformly mixed and applied to an aluminum foil current collector having a thickness of about 20 m; The negative electrode is composed of approximately 90% of a negative electrode active material carbon material, 4% to 5% acetylene black conductive agent, and 6% to 7% binder, and is applied to a copper foil current collector with a thickness of 15 m. The thickness of the positive electrode and the negative electrode is about 0.18 to 0.20 mm, and the middle is separated by a thickness of about 10 m. The separator is generally a polyethylene or polypropylene film, and the electrolyte is an organic carbonate solution of lithium hexafluorophosphate. Remove the used lithium ion secondary battery from its packaging and case, take out the battery cells, and separate the positive electrode material.

Separation technology

1. USP and large-capacity maintenance-free lead-acid battery regeneration protection supplement liquid.

2. In addition to lead acid batteries.

3. Method for processing metal-containing waste.

4. Methods for removing and recovering mercury from waste batteries.

5. A method for recovering valuable metals from waste secondary batteries.

6. A method for recovering valuable substances from waste secondary batteries.

7. Method for extracting zinc and manganese dioxide from waste dry batteries.

8. Method for extracting zinc and manganese dioxide from waste dry batteries.

9. A method for preparing nanometer cobalt oxide from waste lithium ion batteries.

10. A method for recovering negative electrode materials from waste lithium batteries.

11. A method for recovering metals from waste lithium ion batteries.

12. Method for extracting manganese dioxide and zinc from waste zinc-manganese dry batteries.

13. Methods and equipment for obtaining enriched substances from waste batteries.

14. Methods and equipment for separating batteries, coin cells and metals from garbage.

15. A method for recovering metals from used nickel-metal hydride batteries.

16. A method for recovering metals from used nickel-metal hydride batteries.

17. Battery crusher and battery crushing method.

18. Recycling methods of secondary batteries.

19. Waste battery treatment device.

20. Harmless biological pretreatment methods for waste batteries.

21. Comprehensive utilization of waste batteries.

22. Recycling methods of waste dry batteries.

23. Harmless recycling process of waste dry batteries.

24. Waste battery disposal method.

25. Harmless recycling process for waste batteries.

26. Waste battery recycling processor.

27. Recycling and decomposing head of waste battery.

28. Vacuum distillation device for waste battery recycling.

29. Method for recycling used batteries.

30. Waste battery pyrolysis gasification incineration treatment equipment and treatment method thereof.

31. Method for separating and purifying zinc and manganese dioxide in the comprehensive treatment of waste batteries.

32. Comprehensive utilization and treatment of waste batteries.

33. Alkaline leaching of waste dry batteries.

34. Waste dry battery recovery and treatment device.

35. Recycling methods for waste lithium ion batteries.

36. A method for regenerating a used lithium ion secondary battery cathode material.

37. Comprehensive recycling and disposal technology of used mobile phone batteries.

38. Green lead extraction method for waste batteries.

39. Clean recycling method of lead from used batteries.

40. Clean recycling technology for waste battery lead.

41. Waste lead-acid batteries produce recycled lead, red lead and lead nitrate.

42. Lead recycling technology for waste lead batteries.

43. Reduction and transformation method of sludge of waste lead storage battery.

44. Smelting and regeneration furnace for waste lead storage batteries.

45. The smelting of waste battery lead-containing materials is continuously smelted.

46. A method for continuous smelting of a waste battery containing lead-containing materials in a reflex furnace.

47. Treatment and utilization of cadmium-nickel battery waste residue and liquid.

48. Comprehensive recycling method of mercury-containing waste batteries.

49. Comprehensive recycling method of mercury-containing waste dry batteries.

50. Raw materials for chemical power batteries and recycling technology.

51. A method and a device for recovering cadmium by reduction distillation.

52. A method of recycling batteries, especially dry batteries.

53. A method and apparatus for recycling components of a sealed battery.

54. Zinc powder for alkaline batteries.

55. High specific energy amalgam-free zinc powder for alkaline batteries, a preparation method thereof and a device used therefor.

56. Mercury-free and zinc-free powder for alkaline zinc-manganese batteries and production method thereof.

57. Metal-air battery waste recycling device.

58. Recycling dry batteries by leaching.

59. A composition for purifying and treating waste batteries or mercury-containing sludge and a method for treating the same.

60. Waste battery and heavy metal sorting manipulator in garbage processing plant.

61. Waste battery and heavy metal sorting device.

62. Recovery process of n-methylpyrrolidone in waste gas treatment of lithium battery industry.

63. A method for recovering positive electrode scraps and fragments of a lithium ion secondary battery.

64. A method for recovering a positive electrode residual material of a lithium ion secondary battery.

65. A method for preparing manganese zinc ferrite pellets and mixed carbonates by using waste dry batteries.

66. A method for producing metal compounds by using waste zinc-manganese dry batteries.

67. Comprehensive recycling method of nickel-cadmium waste batteries.

68. Manufacturing method of cadmium oxide powder for nickel-cadmium storage battery.

69. A method for recovering positive and negative electrode residual materials of nickel-hydrogen secondary batteries.

70. Lead-acid battery regeneration source and production method.

71. Regeneration technology of lead-acid battery failure.

72. A method for removing sulfate radicals from the plates of waste lead storage batteries.

73. A method for regenerating a negative alloy powder of a failed nickel-hydrogen secondary battery.

74. Technical method for calcining cement clinker to treat waste dry batteries.

75. Zinc-manganese dioxide primary battery electrolyte rapid treatment process.

76. Recycling polytropic agent and treatment process for battery waste plate.

77. Regeneration method of battery desulfurizing agent.

78. An electrolytic manganese dioxide for doped and modified lithium manganese dioxide battery.

79. A method for recovering lead from waste batteries.

80. A method for recycling waste batteries.

81. A crushing device for waste dry batteries.

82. A method for smelting a waste-battery non-polluting reverberatory furnace.

83. A method of refining refined lead by fire.

84. A method for regenerating a battery desulfurizing agent.

85. An improved manganese dioxide for a lithium battery.

86. A method for producing a sewage treatment agent using waste batteries as raw materials.

87. A method for producing active lead powder from waste battery sludge.

88. A method for preparing manganese-zinc ferrite from a waste alkaline manganese dioxide battery.

89. A method for preparing manganese zinc ferrite from waste zinc manganese batteries.

90. A method for separating and recovering lithium from a used lithium ion battery by using an ion sieve.

91. Apparatus and method for nickel and cadmium recovery.

92. A method for preparing ferrite from waste zinc-manganese batteries.

93. A method for recovering lead in a waste battery by electrolytic reduction in a neutral medium.

94. Recover manganese sulfate, manganese dioxide, graphite, and reused graphite electrodes from special waste zinc-manganese dry batteries and their special equipment.

Waste battery treatment method

The treatment method of the waste battery can also start from the structure of the battery. The first is the skin of the surface. Its main component is zinc. There is also such an experiment in the experiment of the third grade:

1. Obtain zinc sulfate crystals from zinc skin of waste battery.

Experimental supplies: beaker, iron stand (with iron ring), alcohol lamp, evaporation dish.

Dilute sulfuric acid, zinc skin for dry batteries.

Experimental steps:

(1) After removing the impurities on the surface of the zinc skin of the dry battery, put them in a beaker.

(2) Pour an appropriate amount of dilute sulfuric acid into the beaker, immerse the zinc skin as the degree, and wait for the zinc skin to dissolve.

(3) Filter the reaction solution.

(4) Pour the filtrate into the evaporation dish, place the evaporation dish on the iron ring of the iron stand, and heat it with an alcohol lamp. When more crystals are deposited in the evaporation dish, stop heating, use the residual heat of the evaporation dish to evaporate the filtrate, recover the zinc sulfate crystals, and place them in the designated container.

2. The ingredients in the second layer of chemicals are very complicated. Only advanced machines can be used to extract the relevant ingredients and make useful things. Japan once also had a factory that recycles waste batteries to extract mercury from it, but a ton of waste batteries can extract dozens of kilograms of mercury at most, so this factory eventually went bankrupt due to large investment and small recovery. Although the government encourages the development of such industries, many manufacturers dare not take risks. The innermost layer is of course the graphite electrode.

3. The innermost part of the battery is a graphite carbon rod, which also has a great effect and has great economic value after recycling. If you remove some powder from graphite and touch it with your hands, it will feel smooth. This property of graphite determines that it can be used as a lubricant. Some machines that work at high temperatures use graphite powder as a lubricant. In addition to the lubricity of graphite powder, it also uses its high melting point and high temperature resistance. In fact, graphite also has another important use, which is to make artificial diamond. Perhaps few people know that graphite and diamond are simple substances composed of carbon elements, but their atomic arrangement order is different, resulting in great differences between them. By heating graphite to 20000C, pressurizing to 5 × 109 Pa to 1 × 1010 Pa, and in the presence of a catalyst, the shiny artificial diamond can be manufactured. When people saw that beautiful diamond, they never thought that it was made of graphite.