Due to the increasing challenges posed by the relentless rise in the design complexity of integrated circuits, Boolean Satisfiability (SAT) has emerged as a robust alternative to structural APTG techniques. However, the high cost of transforming a circuit testing problem to a Conjunctive Normal Form (CNF) limits the application of SAT in industrial ATPG scenarios, resulting in a loss of test coverage. In Order to address this problem, this paper proposes a conflict-driven structural learning (CDSL) ATPG algorithm firstly, in which the conflict-driven heuristic methods in modern SAT solver are implemented on the logic cone of fault propagation and activation directly. The proposed CDSL algorithm is composed of three parts: (1) According to the implication graph, various conflict constraints have been learned to prune search space. (2) Conflict-driven implication and justification have been applied to increase decision accuracy and solving efficiency. (3) A conflict-based diagnosis method is further proposed in the case of low coverage debug, leading to making the aborted faults testable by relaxing or modifying some constraints on primary inputs. Extensive experimental results on industrial circuits demonstrate the effectiveness and efficiency of the proposed CDSL algorithm. It is shown that compared with the SAT-based ATPG, the proposed CDSL can on average decrease $25.6\%$ aborted faults with $94.51\%$ less run time. With a two-stage computational flow, it has shown that the proposed CDSL can lead to $46.37\%$ less aborted faults than a one-stage structural algorithm, further with the $3.19\%$ improvement on fault coverage. In addition, the conflict diagnosis can lead to $8.89\%$ less aborted faults on average, and $0.271\%$ improvement in fault coverage rate.