General Information about the Chemicals content of portable rechargeable batteries. Waste Classification Criteria

Transcription

1 General Information about the Chemicals content of portable rechargeable batteries. Waste Classification Criteria 1. LITHIUM-ION Electrochemical Reaction Li (1-X) CoO 2 + C y Li x === LiCoO 2 + C y 2. NICKEL-METAL HYDRIDE Electrochemical Reaction NiOOH + NiMH === Ni(OH)2 + M 3. NICKEL-CADMIUM Electrochemical Reaction 2 NiOOH + Cd + 2 H2O === 2 Ni(OH)2 + Cd(OH)2 NB. The information reported below concerns the composition of a rechargeable battery in a 50 % charge/discharge state. Conclusions. Among the 3 Sealed Rechargeable Batteries Systems reviewed in this analysis, Ni-Cd and Ni-MH would qualify as Hazardous Waste when the H criteria described in COMMISSION DECISION of 3 May 2000 are applied (Annex B). In accordance with the requirements of waste classification as hazardous these waste battery systems are considered to display one or more of the properties listed in Annex III to Directive 91/ 689/EEC. The Lithium-Ion battery system does not qualify as hazardous waste under those evaluation criteria. Should the new hazard criteria recommended by the Consultant on the revision of the List of Waste apply, the conclusions would not change (Annex C). There would be more justification to classify Nickel-based alkaline batteries as hazardous waste due to the use of R criteria for nickel hydroxide. The absence of official classification of substances used in Li-Ion batteries influences these conclusions. 1

2 1. LITHIUM-ION (Rechargeable Battery) Part 1. Electrochemical Reaction and Composition. Li (1-X) CoO 2 + C y Li x === LiCoO 2 + C y INFORMATION ON COMPOSITION Substances CAS-No. EC-No. Weight % Classification Aluminium % F, R15-17 CyLix (lithium intercalated in graphite) As individual subst ances Graphite % Lithium % F, R14/15, C, R34 DiMethyl-Carbonate % F, R 11, DiEthyl-Carbonate % Not Classified Ethyl-Methyl-Carbonate (?) Not Classified Copper % Not Classified Lithiated Cobalt Oxide % Not Classified (LiCoO2) LiPF % Not Classified Steel % For the full text of the Symbols and R phrases mentioned in this Section, see Appendix A below. For the criteria of waste classification, see Appendix B below. Analysis: The Criteria R 34 is observed for Lithium which is intercalated in a carbon structure and present below the threshold limit of 5 %. Conclusion: Does not qualify as Haz. Waste. 2

3 1. LITHIUM-ION (Rechargeable Battery) PART 2 General description of the composition of a Lithium-Ion rechargeable battery. Rechargeable Lithium Cells (Components) Li-Ion Cylindrical & Prismatic positive contact (top cover) safety vent isolating seal gasket positive current collector Aluminium positive electrode Carbon separator Poly Vinylidene Fluoride 0.5 to 2.0 electrolyte Lithium Hexafluorophosphate 1.0 to 5 solvant Diethyl carbonate 1.0 to 10.0 Methyl Ethyl Carbonate 1.0 to 10.0 negative electrode Graphite 10 to 20 Lithium Cobalt Oxide 20 to 30 negative current collector Copper 5 to 15 housing (negative terminal) Insulator material Plastic Others Steel & others balance TOTAL 100 3

4 2. NICKEL-METAL HYDRIDE (Rechargeable Battery). Electrochemical Reaction. NiOOH + NiMH === Ni(OH)2 + M INFORMATION ON COMPOSITION Substances CAS-No. EC-No. Weight % Classification Nickel hydroxide % Carc. Cat. 3, R40 Sensitizing R 43, Xn R20/22 N R50-53 NiOOH Not classified Nickel Metal Hydride Alloy (Nickel-based) 25-35% Refer to base metals Such as nickel M=Nickel metal Carc.Cat 3, R40 Sensitizing R 43, Potassium hydroxide + water % C, R35, Xn R22 (Used as 30 % in water) Used together with Sodium Hydroxide % Lithium hydroxide % Nickel-plated steel can 20 % Mainly made of steel with a thin layer of Nickel (a few micrometers) For the full text of the Symbols and R phrases mentioned in this Section, see Appendix A below. For the criteria of waste classification, see Appendix B below. Analysis: The criteria R 35 applies to Potassium Hydroxide which is present at a concentration above 1.0 %. The criteria harmful Xn applies to Nickel Hydroxide that is present at a concentration above 25 % by w. Conclusion: Qualified as Haz. Waste. 4

5 3. NICKEL-CADMIUM (Rechargeable Battery) Electrochemical Reaction. 2 NiOOH + Cd + 2 H2O === 2 Ni(OH)2 + Cd(OH)2 INFORMATION ON COMPOSITION Substances CAS-No. EC-No. Weight % Classification 1. Nickel Hydroxide % Carc. Cat 3 R40, Xn R20/22 sensitizing R43, N R Nickel OxyHydroxide Not Classified 3. Cadmium Hydroxide Not Classified 4. Cadmium % Carc Cat 2 R45, N; R Muta Cat 3 R68 Rep Cat 3 R62-63 T R 48/23/25, T+, R26 Potassium hydroxide + water % C, R35, Xn R22 (Used as 30 % in water) Sodium Hydroxide % Lithium hydroxide % Nickel-plated steel can 30/40 % For the full text of the Symbols and R phrases mentioned in this Section, see Appendix A below. For the criteria of waste classification, see Appendix B below. Analysis: The criteria R 35 applies to Potassium Hydroxide which is present at a concentration above 1.0 %. The criteria R 45 applies for Cadmium as Carc. Cat 2. in conc. > 0.1 % as well as criteria R for ReproTox in conc. > 5%. Conclusion: Qualified as Haz. Waste. 5

6 4. Nickel-based Rechargeable Batteries General description of the composition of Nickel-based rechargeable batteries. Rechargeable Alkaline Cells (Components) Ni-Cd (% by weight) Ni-MH (% by weight) positive contact sealing plate isolating seal safety spring valve sealing washer rubber plate positive current collector positive electrode Nickel-based 32 Nickel-based 33 separator electrolyte KOH 2 KOH 2 solvant H2O 8 H2O 8 negative electrode Cadmium-based 15 Rare Earth & other metals 15 negative current collector housing (negative terminal) Ni-Plated steel 30 Ni-plated steel 30 isolating seal Plastic 5 5 Others 8 7 TOTAL

7 APPENDIX A. Risk Phrases The classification below is reported in accordance with Directive 1999/45/EC. C Corrosive F Flammable N Dangerous for the Environment T At low levels cause T+ Very toxic damage to health Xi May cause inflammation to the skin or other mucous membranes Xn Harmful (Health) R11 Highly flammable. R14/15 Contact with water liberates extremely flammable gases. R17 Spontaneously flammable in air. R19 May form explosive peroxides. R20 R22 R26 R35 Harmful by inhalation. Harmful if Swallowed Very toxic by inhalation. Causes severe burns. R40 Limited evidence of a carcinogenic effect. R43 May cause sensitisation by skin contact R42/43 May cause sensitisation by inhalation or skin contact R45 May cause cancer. R49 May cause cancer by inhalation R50/53 Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment R53 May cause long-term adverse effects in the environment R60 R61 R62 R68 May impair fertility May cause harm to the unborn child. Possible risk of impaired fertility. Possible risk of irreversible effects Carc. Cat. 2. Repro. Cat. 2. Muta. Cat. 3. Substances which should be regarded as if they cause cancer in man Substances which should be regarded as if they cause reproductive toxicity in man Substances which cause concerns for mutagenicity in man. For more information see the ECB website Classification and Labelling Annex 1 and Working Database The information provided in this document is correct to the best of our knowledge, information and belief at the date of its publication. The information given is designed only as a guidance. The information relates only to the specific material designated and may not be valid for such material used in combination with any other materials or in any process. 7

8 Appendix B. COMMISSION DECISION of 3 May 2000 replacing Decision 94/3/EC establishing a list of wastes pursuant to Article 1(a) of Council Directive 75/442/EEC on waste and Council Decision 94/904/EC establishing a list of hazardous waste pursuant to Article 1(4) of Council Directive 91/689/EEC on hazardous waste. (notified under document number C(2000) 1147) (Text with EEA relevance) (2000/532/EC) Article 2 Wastes classified as hazardous are considered to display one or more of the properties listed in Annex III to Directive 91/ 689/EEC and, as regards H3 to H8, H10 (6) and H11 of that Annex, one or more of the following: flash point 55 C, one or more substances classified (1) as very toxic at a total concentration 0,1 %, one or more substances classified as toxic at a total concentration 3 %, one or more substances classified as harmful (Xn) at a total concentration 25 %, one or more corrosive substances classified as R35 at a total concentration 1 %, one or more corrosive substances classified as R34 at a total concentration 5 %, one or more irritant substances classified as R41 at a total concentration 10 %, one or more irritant substances classified as R36, R37, R38 at a total concentration 20 %, one or more substances known to be carcinogenic of category 1 or 2 at a total concentration 0,1 %, one or more substances toxic for reproduction of category 1 or 2 classified as R60, R61 at a total concentration 0,5 %, one or more substances toxic for reproduction of category 3 classified as R62, R63 at a total concentration 5 %, one or more mutagenic substances of category 1 or 2 classified as R46 at a total concentration 0,1 %, one or more mutagenic substances of category 3 classified as R40 at a total concentration 1 %. ANNEX List of wastes pursuant to Article 1(a) of Directive 75/442/EEC on waste and Article 1(4) of Directive 91/689/EEC on hazardous waste 5. For the purpose of this Decision, dangerous substance means any substance that has been or will be classified as dangerous in Directive 67/548/EEC as amended; heavy metal means any compound of antimony, arsenic, cadmium, chromium (VI), copper, lead, mercury, nickel, selenium, tellurium, thallium and tin, including these metals in metallic form, as far as these are classified as dangerous substances. 6. If a waste is identified as hazardous by a specific or general reference to dangerous substances, the waste is hazardous only if the concentrations of those substances are such (i.e. percentage by weight) that the waste presents one or more of the properties listed in Annex III to Council Directive 91/689/EEC. As regards H3 to H8, H10 and H11, Article 2 of this Decision applies. For the characteristics H1, H2, H9 and H12 to H14 Article 2 of the present Decision does not provide specifications at present. (1) The classification as well as the R numbers refer to Council Directive 67/548/EEC of 27 June 1967 on the approximation of the laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (OJ 196, , p. 1.) and its subsequent amendments. The concentration limits refer to those laid down in Council Directive 88/ 379/EEC of 7 June 1998 on the approximation of the laws, regulations and administrative provisions of the Member States relating to the classification, packaging and labelling of dangerous preparations (OJ L 187, , p. 14.) and its subsequent amendments. 8

9 ANNEX C. PROPOSAL of the Consultant to the Commission for adapting the H Criteria under the revision of the List of Waste. H14-Criterium Concerning the application of the H14 criterion the consultants propose to link it directly with the criteria in chemicals legislation ( DSD, DPD and GHS) and the following R-phrases in particular: o R50-53 very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment o R50 very toxic to aquatic organisms o R51-53 toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment o R52-53 harmful to aquatic organisms, may cause long-term adverse effects in the aquatic environment o R52 harmful to aquatic organisms o R53 may cause long-term adverse effects in the aquatic environment o R54+ toxic to flora o R55+ toxic to fauna o R56+ toxic to soil organisms o R57+ toxic to bees o R58+ may cause long-term adverse effects in the environ o R59 dangerous for the ozone layer This is going beyond the current scope of the DPD scope, as the terrestrial environment is currently not covered in there. For the concentration limits to be applied to the related R-phrases, they refer to: o Annex III part B of the DPD and specifically o table 1 of annex III part B is mentioned for the acute aquatic toxicity and long term effects o table 5 of annex III part b: Hazards for the ozone layer: For testing a reference was made that for ecotox testing and characterisation of waste the use of biological test batteries and should be further considered for the review of the LOW. It is stated that the basis test battery includes aquatic and terrestrial biotests, for which test specific limit values are defined to identify an ecotoxic signal in the test system. In order to differ between hazardous and non hazardous waste, which means referring the test signal to a hazard classification, the determination of threshold values is intended to be addressed by Germany. Germany proposes the following limit values: 9

10 Proposed draft comment: o The appointment of the H14 criterion should not be based on hazard, but on the actual risk and this could be realised by taking into account: The bioavailability (potential for release); Heterogeneous characteristics of batches of wastes, which doesn t justify a simple treatment as if they were chemicals o We support the possibility to use of biotest batteries and would like to refer to the work that was done under the auspecies of the TAC workgroup, where: Test methods have been evaluated and proven very useful, e.g. S4 test and EN test Ring tests have been conducted to demonstrate their performance. o From the document, it is clear that the focus on approaching classification of wastes is mainly bases on disposal in landfills, while e.g. for metals a lot recovery and recycling is taking place because of the fact that metals are a valuable resource for industry with a high value. 10