Codeofchina.com is in charge of this English translation. In case of any doubt about the English translation, the Chinese original shall be considered authoritative.
This document is developed in accordance with the rules given in GB/T 1.1-2020 Directives for standardization - Part 1: Rules for the structure and drafting of standardizing documents.
Attention is drawn to the possibility that some content of this document may involve patents. The issuing body of this document shall not be held responsible for identifying any or all such patent rights.
This document was proposed by China Nonferrous Metals Industry Association.
This document is under the jurisdiction of SAC/TC 243 National Technical Committee on Nonferrous Metals of Standardization Administration of China.
Recycled black mass for lithium ion battery
1 Scope
This document specifies the classification and grading, technical requirements, test methods, inspection rules, marking, packaging, transportation, storage and accompanying documents of recycled black mass for lithium ion battery.
This document is applicable to battery black mass prepared through recycling of lithium ion battery scraps and used for subsequent recycling.
2 Normative references
The following documents contain provisions which, through reference in this text, constitute provisions of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.
GB/T 191 Packaging - Pictorial marking for handling of goods
GB/T 8170 Rules of rounding off for numerical values & expression and judgment of limiting values
YS/T 1342 (all parts) Methods for chemical analysis of waste secondary battery
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
lithium ion battery scraps
waste lithium ion batteries and their waste raw materials
Note: Scrap lithium ion batteries, scrap semi-finished products and waste raw materials generated during the industrial production, and lithium ion batteries that have lost their use value in daily life or circulation are included.
3.2
black mass
black or gray-black mass composed of one or more valuable components such as lithium, nickel and cobalt, which is obtained through processes such as discharge, disassembly, pyrolysis, crushing and sorting by taking lithium ion battery scraps as raw material
[Source: QC/T 1156-2021, 3.4, modified]
3.3
acid-insoluble substance
acid-insoluble substance in black mass
Note: Inclusions such as graphite, diaphragm and binder are included.
4 Classification and grading
4.1 Classification
The products are classified into Class I and Class II according to different types of cathode materials in the raw materials of the products:
——Class I: products made from lithium ion battery scraps containing nickel or (and) cobalt;
——Class II: products made from lithium ion battery scraps containing lithium iron phosphate.
4.2 Grading
The products are classified into Grade I and Grade II according to different sources of raw materials of the products:
——Grade I: products made from anode piece scraps;
——Grade II: products made from battery as scraps.
5 Technical requirements
5.1 Chemical composition
5.1.1 The contents of main elements and water-soluble fluoride in the product shall meet those specified in Table 1.
Table 1 Chemical composition (dry basis)
Chemical composition (mass fraction)/% Class I Class II
Grade I Grade II Grade I Grade II
Lithium ≥6.00 ≥3.50 ≥4.00 ≥2.00
Total nickel-cobalt content ≥45.00 ≥25.00 ≤1.00
Iron — ≥28.00 ≥18.00
Phosphorus ≤0.80 ≥15.00 ≥10.00
Manganese — —
Water-soluble fluoride ≤0.10 ≤0.40 ≤0.10 ≤0.10
5.1.2 The total water-leachable organic carbon (TOC) in the product should not be greater than 0.10%.
5.1.3 The acid-insoluble substance in Grade I product should not exceed 5.00%, and that in Class I and Class II products should not exceed 40.00% and 45.00% respectively.
5.2 Weight loss on drying
The weight loss on drying of the product should not be greater than 2.0%.
5.3 Admixtures or inclusions
5.3.1 No other scrap materials shall be mixed into the product. The molar ratios of the main element lithium to nickel, cobalt and manganese in Class I products shall be within 0.95 and 1.10 respectively, and the molar ratios of the main element lithium to phosphorus and iron in Class II products shall be within 0.95 and 1.10 respectively; at the same time, the zinc content shall not be greater than 0.10%, and the contents of lead, cadmium, chromium and arsenic shall not be greater than 0.01% respectively.
5.3.2 There shall be no visible inclusions, and the mass fraction of the oversize product of 60-mesh sieve shall not be greater than 1.0%.
6 Test methods
6.1 Chemical composition
6.1.1 The methods for determining the nickel, cobalt, manganese, lithium, phosphorus and iron contents in the product shall be in accordance with Annex A, YS/T 1342 (all parts), Annex B and Annex C respectively. During the arbitration, the contents of main elements such as nickel, cobalt, manganese and lithium in the product shall be in accordance with YS/T 1342 (all parts), and the contents of the main elements such as phosphorus and iron in the product shall be in accordance with Annex B and Annex C respectively.
6.1.2 The determination of water-soluble fluoride content in the product shall be in accordance with Annex D.
6.1.3 The method for determining the total water-leachable organic carbon (TOC) content in the product is shown in Annex E.
6.1.4 The method for determining the acid-insoluble substance content in the product is provided in Annex F.
6.2 Weight loss on drying
The method for determining the weight loss on drying in the product is shown in Annex G.
6.3 Admixtures or inclusions
6.3.1 The methods for calculating the molar ratios of main elements in the product is shown in Annex H. The methods for determining the zinc, lead, chromium, cadmium and arsenic contents in the product are shown in Annex A.
6.3.2 Inclusions are inspected visually, and the method for determining the particle size of the product is shown in Annex I.
7 Inspection rules
7.1 Inspection and acceptance
7.1.1 The product shall be inspected by the supplier or the third-party inspection department, and the supplier shall ensure that the product quality conforms to the requirements of this document.
7.1.2 The purchaser shall inspect the received product according to those specified hereof; if the inspection result is inconsistent with the requirements hereof, the condition shall be proposed to the supplier within 30d from the day of receiving the product, and settled through negotiation by the supplier and the purchaser. If the arbitration is required, the sampling shall be jointly conducted by the supplier and the purchaser at the purchaser's or agreed through negotiation.
7.2 Batching
Each batch of products shall be composed of products of the same class and grade, and shall not exceed 32t. The batching method shall be carried out according to the incoming batches of the supplier or determined through on-site negotiation by the supplier and the purchaser.
7.3 Inspection items
Each batch of products shall be tested for chemical composition, weight loss on drying, admixtures or inclusions.
7.4 Sampling
7.4.1 The sampling of products shall meet those specified in Table 2.
Table 2 Sampling
Inspection item Sampling requirements Clause/subclause No. of technical requirements Clause/subclause No. of test method
Chemical composition 7.4.2 to 7.4.4 5.1 6.1
Weight loss on drying 5.2 6.2
Admixtures or inclusions 5.3 6.3
7.4.2 Each batch of products is randomly sampled according to not less than 50% of the package quantity, and the number of sampling bags is not less than 10; when the package quantity is less than 10 bags, all bags shall be sampled.
7.4.3 During sampling, the sampling points of each bag shall be uniformly distributed into top, middle and bottom parts according to any diagonal line on the side of the packaging bag. The sampling borer (about 800mm in length and 50mm±2mm in inner diameter φ) shall be inserted flat to 3/4 the depth of the material layer for sampling, rotated 180° and then drawn out, and shall be full of materials. The sample of each time shall be packed in a plastic bag and sealed in time.
7.4.4 All samples of each batch shall be thoroughly mixed, and each sample shall be divided into four portions by quartering method (with each portion of not less than 2kg), respectively packed into four clean sealed containers, and then attached with labels (indicating the number, class, grade, place of origin, sampling and preparation personnel, sampling date and analysis item). One portion is used as the acceptance analysis sample, two for the purchaser and the supplier respectively, and the last as the arbitration sample signed by the parties on site. The arbitration sample shall be kept by the purchaser for a period of three months generally.
7.5 Judgment of inspection results
7.5.1 The inspection result is rounded off according to GB/T 8170, and judged using the rounded-off-value comparison method.
7.5.2 If the inspection result of any index fails to meet the requirements hereof, the batch of products will be judged as unacceptable.
Foreword i 1 Scope 2 Normative references 3 Terms and definitions 4 Classification and grading 5 Technical requirements 6 Test methods 7 Inspection rules 8 Marking, packaging, transportation, storage and accompanying documents Annex A (Informative) Determination of nickel, cobalt, manganese, lithium, phosphorus, iron, zinc, lead, cadmium, chromium and arsenic contents in recycled black mass for lithium ion battery - Inductively coupled plasma atomic emission spectrometry Annex B (Normative) Determination of phosphorus content in recycled black mass for lithium ion battery - Quinoline phosphomolybdate gravimetric method Annex C (Normative) Determination of iron content in recycled black mass for lithium ion battery - Titanium trichloride reduction potassium dichromate titration method Annex D (Normative) Determination of water-soluble fluoride content in recycled black mass for lithium ion battery - Fluoride ion selective electrode method Annex E (Informative) Determination of water-leachable total organic carbon content in recycled black mass for lithium ion battery - Combustion oxidation ⁃ Non-dispersive infrared absorption method Annex F (Informative) Determination of acid-insoluble substance content in recycled black mass for lithium ion battery - Gravimetric method Annex G (Informative) Determination of weight loss on drying of recycled black mass for lithium ion battery - Loss-on-drying method Annex H (Informative) Calculation method for molar ratio of main elements in recycled black mass for lithium ion battery Annex I (Informative) Determination of particle size of recycled black mass for lithium ion battery - Sieving and weighing method Bibliography
Codeofchina.com is in charge of this English translation. In case of any doubt about the English translation, the Chinese original shall be considered authoritative.
This document is developed in accordance with the rules given in GB/T 1.1-2020 Directives for standardization - Part 1: Rules for the structure and drafting of standardizing documents.
Attention is drawn to the possibility that some content of this document may involve patents. The issuing body of this document shall not be held responsible for identifying any or all such patent rights.
This document was proposed by China Nonferrous Metals Industry Association.
This document is under the jurisdiction of SAC/TC 243 National Technical Committee on Nonferrous Metals of Standardization Administration of China.
Recycled black mass for lithium ion battery
1 Scope
This document specifies the classification and grading, technical requirements, test methods, inspection rules, marking, packaging, transportation, storage and accompanying documents of recycled black mass for lithium ion battery.
This document is applicable to battery black mass prepared through recycling of lithium ion battery scraps and used for subsequent recycling.
2 Normative references
The following documents contain provisions which, through reference in this text, constitute provisions of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.
GB/T 191 Packaging - Pictorial marking for handling of goods
GB/T 8170 Rules of rounding off for numerical values & expression and judgment of limiting values
YS/T 1342 (all parts) Methods for chemical analysis of waste secondary battery
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
lithium ion battery scraps
waste lithium ion batteries and their waste raw materials
Note: Scrap lithium ion batteries, scrap semi-finished products and waste raw materials generated during the industrial production, and lithium ion batteries that have lost their use value in daily life or circulation are included.
3.2
black mass
black or gray-black mass composed of one or more valuable components such as lithium, nickel and cobalt, which is obtained through processes such as discharge, disassembly, pyrolysis, crushing and sorting by taking lithium ion battery scraps as raw material
[Source: QC/T 1156-2021, 3.4, modified]
3.3
acid-insoluble substance
acid-insoluble substance in black mass
Note: Inclusions such as graphite, diaphragm and binder are included.
4 Classification and grading
4.1 Classification
The products are classified into Class I and Class II according to different types of cathode materials in the raw materials of the products:
——Class I: products made from lithium ion battery scraps containing nickel or (and) cobalt;
——Class II: products made from lithium ion battery scraps containing lithium iron phosphate.
4.2 Grading
The products are classified into Grade I and Grade II according to different sources of raw materials of the products:
——Grade I: products made from anode piece scraps;
——Grade II: products made from battery as scraps.
5 Technical requirements
5.1 Chemical composition
5.1.1 The contents of main elements and water-soluble fluoride in the product shall meet those specified in Table 1.
Table 1 Chemical composition (dry basis)
Chemical composition (mass fraction)/% Class I Class II
Grade I Grade II Grade I Grade II
Lithium ≥6.00 ≥3.50 ≥4.00 ≥2.00
Total nickel-cobalt content ≥45.00 ≥25.00 ≤1.00
Iron — ≥28.00 ≥18.00
Phosphorus ≤0.80 ≥15.00 ≥10.00
Manganese — —
Water-soluble fluoride ≤0.10 ≤0.40 ≤0.10 ≤0.10
5.1.2 The total water-leachable organic carbon (TOC) in the product should not be greater than 0.10%.
5.1.3 The acid-insoluble substance in Grade I product should not exceed 5.00%, and that in Class I and Class II products should not exceed 40.00% and 45.00% respectively.
5.2 Weight loss on drying
The weight loss on drying of the product should not be greater than 2.0%.
5.3 Admixtures or inclusions
5.3.1 No other scrap materials shall be mixed into the product. The molar ratios of the main element lithium to nickel, cobalt and manganese in Class I products shall be within 0.95 and 1.10 respectively, and the molar ratios of the main element lithium to phosphorus and iron in Class II products shall be within 0.95 and 1.10 respectively; at the same time, the zinc content shall not be greater than 0.10%, and the contents of lead, cadmium, chromium and arsenic shall not be greater than 0.01% respectively.
5.3.2 There shall be no visible inclusions, and the mass fraction of the oversize product of 60-mesh sieve shall not be greater than 1.0%.
6 Test methods
6.1 Chemical composition
6.1.1 The methods for determining the nickel, cobalt, manganese, lithium, phosphorus and iron contents in the product shall be in accordance with Annex A, YS/T 1342 (all parts), Annex B and Annex C respectively. During the arbitration, the contents of main elements such as nickel, cobalt, manganese and lithium in the product shall be in accordance with YS/T 1342 (all parts), and the contents of the main elements such as phosphorus and iron in the product shall be in accordance with Annex B and Annex C respectively.
6.1.2 The determination of water-soluble fluoride content in the product shall be in accordance with Annex D.
6.1.3 The method for determining the total water-leachable organic carbon (TOC) content in the product is shown in Annex E.
6.1.4 The method for determining the acid-insoluble substance content in the product is provided in Annex F.
6.2 Weight loss on drying
The method for determining the weight loss on drying in the product is shown in Annex G.
6.3 Admixtures or inclusions
6.3.1 The methods for calculating the molar ratios of main elements in the product is shown in Annex H. The methods for determining the zinc, lead, chromium, cadmium and arsenic contents in the product are shown in Annex A.
6.3.2 Inclusions are inspected visually, and the method for determining the particle size of the product is shown in Annex I.
7 Inspection rules
7.1 Inspection and acceptance
7.1.1 The product shall be inspected by the supplier or the third-party inspection department, and the supplier shall ensure that the product quality conforms to the requirements of this document.
7.1.2 The purchaser shall inspect the received product according to those specified hereof; if the inspection result is inconsistent with the requirements hereof, the condition shall be proposed to the supplier within 30d from the day of receiving the product, and settled through negotiation by the supplier and the purchaser. If the arbitration is required, the sampling shall be jointly conducted by the supplier and the purchaser at the purchaser's or agreed through negotiation.
7.2 Batching
Each batch of products shall be composed of products of the same class and grade, and shall not exceed 32t. The batching method shall be carried out according to the incoming batches of the supplier or determined through on-site negotiation by the supplier and the purchaser.
7.3 Inspection items
Each batch of products shall be tested for chemical composition, weight loss on drying, admixtures or inclusions.
7.4 Sampling
7.4.1 The sampling of products shall meet those specified in Table 2.
Table 2 Sampling
Inspection item Sampling requirements Clause/subclause No. of technical requirements Clause/subclause No. of test method
Chemical composition 7.4.2 to 7.4.4 5.1 6.1
Weight loss on drying 5.2 6.2
Admixtures or inclusions 5.3 6.3
7.4.2 Each batch of products is randomly sampled according to not less than 50% of the package quantity, and the number of sampling bags is not less than 10; when the package quantity is less than 10 bags, all bags shall be sampled.
7.4.3 During sampling, the sampling points of each bag shall be uniformly distributed into top, middle and bottom parts according to any diagonal line on the side of the packaging bag. The sampling borer (about 800mm in length and 50mm±2mm in inner diameter φ) shall be inserted flat to 3/4 the depth of the material layer for sampling, rotated 180° and then drawn out, and shall be full of materials. The sample of each time shall be packed in a plastic bag and sealed in time.
7.4.4 All samples of each batch shall be thoroughly mixed, and each sample shall be divided into four portions by quartering method (with each portion of not less than 2kg), respectively packed into four clean sealed containers, and then attached with labels (indicating the number, class, grade, place of origin, sampling and preparation personnel, sampling date and analysis item). One portion is used as the acceptance analysis sample, two for the purchaser and the supplier respectively, and the last as the arbitration sample signed by the parties on site. The arbitration sample shall be kept by the purchaser for a period of three months generally.
7.5 Judgment of inspection results
7.5.1 The inspection result is rounded off according to GB/T 8170, and judged using the rounded-off-value comparison method.
7.5.2 If the inspection result of any index fails to meet the requirements hereof, the batch of products will be judged as unacceptable.
Contents of GB/T 45203-2024
Foreword i
1 Scope
2 Normative references
3 Terms and definitions
4 Classification and grading
5 Technical requirements
6 Test methods
7 Inspection rules
8 Marking, packaging, transportation, storage and accompanying documents
Annex A (Informative) Determination of nickel, cobalt, manganese, lithium, phosphorus, iron, zinc, lead, cadmium, chromium and arsenic contents in recycled black mass for lithium ion battery - Inductively coupled plasma atomic emission spectrometry
Annex B (Normative) Determination of phosphorus content in recycled black mass for lithium ion battery - Quinoline phosphomolybdate gravimetric method
Annex C (Normative) Determination of iron content in recycled black mass for lithium ion battery - Titanium trichloride reduction potassium dichromate titration method
Annex D (Normative) Determination of water-soluble fluoride content in recycled black mass for lithium ion battery - Fluoride ion selective electrode method
Annex E (Informative) Determination of water-leachable total organic carbon content in recycled black mass for lithium ion battery - Combustion oxidation ⁃ Non-dispersive infrared absorption method
Annex F (Informative) Determination of acid-insoluble substance content in recycled black mass for lithium ion battery - Gravimetric method
Annex G (Informative) Determination of weight loss on drying of recycled black mass for lithium ion battery - Loss-on-drying method
Annex H (Informative) Calculation method for molar ratio of main elements in recycled black mass for lithium ion battery
Annex I (Informative) Determination of particle size of recycled black mass for lithium ion battery - Sieving and weighing method
Bibliography